Pyrazol-4-ylbenzoyl derivatives and their use as herbicides

ABSTRACT

Pyrazol-4-ylbenzoyl derivatives                    
     where the substituents L, M, X, Y and n have the meanings given in claim  1  and 
     Q is a pyrazole ring, linked in the 4-position, of the formula II                    
     where 
     R 15  is C 1 -C 4 -alkyl, 
     R 16  is hydrogen, C 1 -C 4 -alkyl or C 1 -C 4 -haloalkyl and 
     R 17  is hydrogen, C 1 -C 4 -alkylsulfonyl, phenylsulfonyl or alkylphenylsulfonyl, 
     where, in the event that Y=C═O, X is other than NR 23 , 
     agriculturally useful salts, a process for their preparation, and their use as herbicides.

The present invention relates to novel herbicidally active pyrazol-4-ylbenzoyl derivatives, to processes for the preparation of the pyrazol-4-ylbenzoyl derivatives, to compositions which comprise them, and to the use of these derivatives or of the compositions comprising them for controlling weeds.

Herbicidally active pyrazolebenzoyl derivatives have been disclosed in the literature, for example in EP 352543, WO 93/15060, WO 94/01431 and WO 93/18031.

However, the herbicidal properties of the known compounds and the compatibility with crop plants are only moderately satisfactory.

It was an object of the present invention to find novel pyrazolebenzoyl derivatives which have improved properties.

We have found that this object is achieved by pyrazol-4-ylbenzoyl derivatives of the formula I

where the substituents have the following meanings:

L,M are hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, it being possible for these groups to be unsubstituted or substituted by one to five halogen atoms or C₁-C₄-alkoxy; halogen, cyano, nitro, a group —(A)_(m)—S(O)_(n)R¹ or a group —(A)_(m)—CO—R²;

Y is a group consisting of C═O, C═N—R³, CR⁷—NR⁵R⁶, CR⁷—OR⁸, CR¹⁰R¹¹, CR⁷—SR⁸; 1,3-dioxanyl or 1,3-dioxolanyl, each of which is substituted by hydrogen or C₁-C₄-alkyl; a hetero atom selected from the group consisting of oxygen, sulfur and nitrogen;

X is a chain (—CR¹²R¹³—), (—CR¹²R¹³—CR²¹R²²—), (—CR¹²═CR¹³—), (—CR¹²R¹³—CR¹²═CR¹³—); NR²³;

the bond between X and Y can be saturated or unsaturated;

A is oxygen or NR¹⁴;

m is zero or one;

n is zero, one or two;

R¹ is C₁-C₄-alkyl, C₁-C₄-haloalkyl or NR¹⁴;

R² is C₁-C₄ alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy or NR¹⁴;

R³ is hydrogen, —NR⁹R⁴; C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₂-C₆-alkenyl, C₂-C₆-haloalkenyl, C₂-C₆-alkynyl;

mono- to polysubstituted phenyl, it being possible for the substituents to be from the series consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano, nitro; mono- to polysubstituted benzyl, it being possible for the substituents to be from the series consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano, nitro;

mono- to polysubstituted benzyloxy, it being possible for the substituents to be from the series consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano, nitro;

R⁴ is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C═O—NR¹⁴;

mono- to polysubstituted phenyl, it being possible for the substituents to be from the series consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano, nitro;

mono- to polysubstituted benzyl, it being possible for the substituents to be from the series consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano, nitro;

R⁹ is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C═O—NR¹⁴;

mono- to polysubstituted phenyl, it being possible for the substituents to be from the series consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano, nitro;

mono- to polysubstituted benzyl, it being possible for the substituents to be from the series consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano, nitro;

R⁵,R⁶ independently of one another are hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₁-C₄ haloalkyl, C₂-C₆ haloalkenyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy;

mono- to polysubstituted phenyl, it being possible for the substituents to be from the series consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano, nitro;

mono- to polysubstituted benzyl, it being possible for the substituents to be from the series consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano, nitro;

R⁷ is hydrogen, C₁-C₆-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy; unsubstituted or substituted phenyl, it being possible for the substituents to be from the series consisting of one to three halogens, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, nitro; R⁷ and R²¹ or R⁷ and R²³ or R⁷ and R¹² can form a bond;

R⁸ is hydrogen, C₁-C₆ alkyl, C₁-C₄-haloalkyl, substituted phenyl, it being possible for the substituents to be from the series consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano, nitro;

substituted benzyl, it being possible for the substituents to be from the series consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano, nitro;

R¹⁰,R¹¹ independently of one another are hydrogen, C₁-C₆-alkyl; phenyl which is unsubstituted or substituted by one to three halogens, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, nitro; R¹⁰ and R¹² or R¹⁰ and R²³ or R¹⁰ and R²¹ can form a bond;

R¹²,R¹³ independently of one another are hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy;

unsubstituted or substituted phenyl, it being possible for the substituents to be from the series consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano, nitro;

R¹⁴ is C₁-C₄-alkyl;

R²¹ is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy; unsubstituted or substituted phenyl, it being possible for the substituents to be from the series consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano, nitro;

R²² is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy; unsubstituted or substituted phenyl, it being possible for the substituents to be from the series consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano, nitro;

R²³ is hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₁-C₆-alkoxy; phenyl or benzyl, each of which is unsubstituted or substituted by C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano, nitro;

Q is a pyrazole ring, linked in the 4-position, of the formula II

where

R¹⁵ is C₁-C₄-alkyl,

R¹⁶ is hydrogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl and

R¹⁷ is hydrogen, C₁-C₄-alkylsulfonyl, phenylsulfonyl or alkylphenylsulfonyl,

where, in the event that Y=C═O, X is other than NR²³,

and agriculturally useful salts of the compound I.

Compounds of the formula I are obtained by reacting 5-hydroxypyrazoles of the formula IIa with a benzoic acid derivative of the formula III and subjecting the products to a rearrangement reaction to give pyrazol-4-ylbenzoyl derivatives of the formula I:

DIAGRAM 1

In the above diagram 1, T in the abovementioned formulae has the meanings of halogen or OH and R¹⁵, R¹⁶, L, M, X, Y and n have the abovementioned meanings.

The first step of the reaction sequence, ie. the acylation, is carried out in the generally known manner, for example by adding an acid chloride of the formula III (T═Cl) or a carboxylic acids III (T═OH) which has been activated using, for example, DCC (dicyclocarbodiimides) or similar agents known from the literature, eg. triphenylphosphine/DEAD=diethyl azodicarboxylate, 2-pyridine disulfide/triphenylphosphine, to the solution or suspension of a cyclohexanedione II, in the presence or absence of an auxiliary base. The reactants and the auxiliary base are expediently employed in equimolar amounts. Under certain circumstances, a slight excess, for example, 1.2 to 1.5 mol equivalents of the auxiliary base, based on II, may be advantageous.

Useful auxiliary bases are tertiary alkylamines, pyridine or alkali metal carbonates. Solvents which can be employed are, for example, methylene chloride, dioxane, diethyl ether, toluene, acetonitrile or ethyl acetate.

While the acid chloride is added, the reaction mixture is preferably cooled to 0 to 10° C., and it is then stirred at from 20 to 100° C., in particular 25 to 50° C., until the reaction has ended. Work-up is carried out in the customary manner, for example the reaction mixture is poured into water and the product of interest is extracted, for example using methylene chloride. After drying of the organic phase and removal of the solvent, the crude enol ester can be employed in the rearrangement reaction without further purification. Preparation examples of benzoic esters of 5-hydroxypyrazoles can be found, for example, [lacuna] EP-A-282 944 or U.S. Pat. No. 4,643,757.

The rearrangement of the 5-hydroxypyrazoylbenzoic [sic] esters to the compounds of the formula I is expediently carried out at from 20 to 40° C. in a solvent and in the presence of an auxiliary base and, if desired, with the aid of a cyano compound as catalyst.

Examples of solvents which can be used are acetonitrile, methylene chloride, tert-amyl alcohol, dioxane, 1,2-dichloroethane, ethyl acetate or toluene. Preferred solvents are acetonitrile and dioxane. Useful auxiliary bases are tertiary alkylamines, pyridine or alkali metal carbonates, and these are preferably employed in equimolar amounts or up to an excess of four times based on the 5-hydroxypyrazolebenzoic [sic] ester. Preferred auxiliary bases are triethylamine and alkali metal carbonate in twice the amount.

Useful catalysts are potassium cyanide, acetone cyanohydrin and trimethylsilyl cyanide, preferably in an amount of 1 to 50 mol percent based on the enol ester. It is preferred to add acetone cyanohydrin, for example in an amount of 5 to 15, in particular 10, mol percent.

Examples of the rearrangement of benzoic esters of 5-hydroxypyrazoles can be found, for example, in EP-A 282 944 or U.S. Pat. No. 4,643,757, but these publications only mention the use of potassium carbonate or sodium carbonate in dioxane as catalyst. While the use of potassium cyanide or acetone cyanohydrin has been disclosed in connection with the similar rearrangement of enol esters of cyclohexane-1,3-diones (U.S. Pat. No. 4,695,673), the literature does not disclose any examples of cyanide compounds being especially useful for a Fries rearrangement of O-acyl derivatives of 5-hydroxypyrazole.

Work-up is carried out in a manner known per se, for example the reaction mixture is acidified with dilute mineral acids such as 5% strength hydrochloric acid or sulfuric acid and extracted using an organic solvent such as methylene chloride or ethyl acetate. For purification, the extract is extracted using cold 5 to 10% strength alkali metal carbonate solution, the end product being concentrated in the aqueous phase. The product of the formula Ia-Ie is precipitated by acidifying the aqueous solution or reextracted using methylene chloride or ethyl acetate, dried and subsequently freed from the solvent.

Those 5-hydroxypyrazoles of the formula II, used as starting material, which are not already known can be prepared by processes known per se (cf. EP-A 240 001 and J. Prakt. Chem. 315, 382 (1973)). 1,3-Dimethyl-5-hydroxypyrazole is a commercially available compound.

Benzoic acids of the formula III can be prepared as follows:

Benzoyl halides such as, for example, benzoyl chlorides of the formula III (T=Cl) are prepared in a manner known per se by reacting the benzoic acids of the formula III (T=OH) with thionyl chloride.

The benzoic acids of the formula III (T=OH) can be prepared in a known manner from the corresponding esters of the formula III (T=C₁-C₄-alkoxy) by means of acidic or basic hydrolysis.

Those intermediates of the formula III which are not already known can be prepared by processes known from the literature.

DIAGRAM 2

For example, as shown in diagram 2, arylthio compounds IV can thus be reacted with substituted haloalkenyl as described in J. Med. Chem. 1984, 27, 1516, with substituted alkynylcarboxylic acids as described in J. Org. Chem. 1980, 45, 4611 or J. Am. Chem. Soc. 1983, 105, 883, with substituted haloalkylcarboxylic acids as described in Chem. Ber. 1925, 58, 1612 in the presence of a base such as alkali metal hydroxide, alkali metal hydride or alkali metal carbonate. The resulting compounds V are cyclized to VI under Friedel-Crafts conditions with an addition of a Lewis acid or a protonic acid. Preferred, as described in Can. J. Chem. 1981, 59, 199; Chem. Ber. 1925, 58, 1625; Chem. Ber. 1926, 59, 1074; Phosp. and Sulf. 1984, 19, 31 are AlCl₃ or SnCl₄ as Lewis acids, and polyphoshoric [sic] acid and sulfuric acid as protonic acid.

Thiochromenone acids can furthermore be synthesized for example by eliminating hydrogen halide from 3-halothiochromanone acids or, for example, by reacting the substituted thiophenolic acids with substituted α-alkyl acetoacetates in the presence of phosphorus pentoxide as described in Ann. Chem. 1964, 680, 40.

The arylthio compounds IV can be obtained, for example, from corresponding anilines by means of a Sandmeyer reaction, and these anilines, in turn, are synthesized by reducing suitable nitro compounds as described in Organikum, 19th edition 1992, 552 et seq.

In the event that, for example, X equals (—CR¹²R¹³—) or (—CR¹²R¹³CR²¹R²²—), Y equals C═O and T equals C₁-C₄-alkoxy, the thiochromanone ester or dihydrobenzothiophene ester can be prepared as described in diagram 2 by alkylating the arylthio compound IV with halopropionic acid or haloacetic acid in the presence of one of the abovementioned bases in solvent or water and the product cyclized to give VI.

The reactants and the base are expediently employed in equimolar amounts. The reaction mixture is stirred, preferably at 20-100° C., in particular at 20-40° C. Working-up is carried out, for example, in such a manner that the reaction mixture is poured into water, the aqueous phase is acidified using mineral acids such as hydrochloric acid or sulfuric acid, and the product of interest is filtered off with suction or extracted by means of extraction with methylene chloride or ethyl acetate, dried and freed from the solvent. The ester can be reacted without further purification.

Stirring V into, for example, polyphosphoric acid at 40-140° C., in particular at 70-100° C., or activating the carboxylic acid by converting it into its acid chloride and stirring with 2-6, in particular 3.5 to 4.5, mol equivalents of a Lewis acid, eg. AlCl₃ or SnCl₄, in a solvent or stirring with or in sulfuric acid gives, after work-up in a manner known per se, ie. adding icewater and removing the product of interest by filtration with suction or extraction of the aqueous phase using ethyl acetate or methylene chloride, drying and removing the solvent, an intermediate of the formula III.

In the event that, for example, X equals an ethylene group (—CR¹²═CR¹³—), Y equals C═O and T equals C₁-C₄-alkoxy, the thiochromenone ester can be reacted for example by reacting an arylthio compound with an acetylenecarboxylic acid derivative in water or solvent at from 0 to 140° C. Work-up is carried out in a manner known per se by adding water and dilute mineral acid, such as hydrochloric acid. The product of interest is either filtered off with suction or obtained by extraction using methylene chloride or ethyl acetate, followed by drying and removing the solvent.

The intermediates of the formula III can be functionalized further by reactions known from the literature, such as reduction as described by Jerry March “1 Advanced organic Chemistry, Fourth Ed., for example p. 910 et seq., oximation as described by Jerry March” Advanced Organic Chemistry, Fourth Ed., for example p. 934, 935, 1039, 1226, 405 et seq., conversion into imines and amines as described by Jerry March “Advanced Organic Chemistry, Fourth Ed., ketalization, alkylation, halogenation, elimination and oxidation as described by Jerry March” Advanced Organic Chemistry, Fourth Ed.

Starting from corresponding saccharine derivatives or 1,2-benzoisothiazoles, the acids of the 3-alkoxy-1,2-benzoisothiazole 1,1-dioxides or 3-alkoxy-1,2-benzoisothiazoles can be obtained, for example, by reaction with PCl₅, POCl₃ or chlorine and alcohol, in the presence or absence of an auxiliary base, eg. triethylamine, which is described, for example, in U.S. Pat. No. 4,571,429, Arch. Pharm. 1984, 317, 807, U.S. Pat. No. 4,461,901, U.S. Pat. No. 450,916, J. Med. Chem. 1986, 29, 359. Saccharine carboxylic acids can be obtained by processes known from the literature as described in Ann. Chem. 427, 231, 1922, Chem. Ber. 13, 1554, 1980, Chem. Ber. 25, 1740, 1892, DE-OS 3607343, German Patent Application P 44 27 995.7.

Those benzo-1,4-oxathiine acid derivatives which are not already known, for example from J. Org. Chem. 1968, 33, 456, can be synthesized from the corresponding phenol derivatives, for example, by reaction as described in Chem. Comm., 1975, 451, J. Org. Chem. 1974, 39, 1811, J. Am. Chem. Soc. 1954, 76, 1068 or by combination of, for example, substitution reaction on halogen-substituted thiophenol derivatives and subsequent reactions, eg. oxidation, reduction or addition as described in J. Het. Chem. 1983, 20, 867.

The benzoic acids of the formula III can also be obtained by reacting the corresponding bromine- or iodine-substituted compound of the formula VII

DIAGRAM 3

T is OH, C₁-C₄-alkoxy and

Y,L,M,X have the meanings described above

with carbon monoxide and water under elevated pressure in the presence of a palladium, nickel, cobalt or rhodium transition metal catalyst and of a base.

The catalysts nickel, cobalt, rhodium and, in particular, palladium can be present in the form of metals or in the form of customary salts, such as in the form of halogen compounds, eg. PdCl₂, RhCl₃.H₂O, acetates, eg. Pd(OAc)₂, cyanides and the like at the known valency levels. Metal complexes with tertiary phosphines, metal alkyl carbonyls, metal carbonyls, eg. CO₂(CO)₈, Ni(CO)₄, metal carbonyl complexes with tertiary phosphines, eg. [P(Ph)₃]₂Ni(CO)₂, or with transition metal salts complexed with tertiary phosphines, may furthermore be present. The latter embodiment is preferred in particular in the case of palladium as the catalyst. The nature of the phosphine ligands varies within wide limits. For example, they can be represented by the following formulae:

where n is the numbers 1, 2, 3 or 4 and the radicals R²⁴ to R²⁶ are low-molecular-weight alkyl, eg. C₁-C₆-alkyl, aryl, C₁-C₄-alkylaryl, eg. benzyl, phenethyl or aryloxy. Aryl is, for example, naphthyl, anthryl and, preferably, unsubstituted or substituted phenyl, where the substituents can be varied within a wide range as long as their being inert to the carboxylation reaction is taken into consideration and comprise all inert C-organic radicals such as C₁-C₆-alkyl radicals, eg. methyl, carboxyl radicals such as COOH, COOM (M is, for example, an alkali metal salt, alkaline earth metal salt or ammonium salt), or C-organic radicals which are bonded via oxygen, such as C₁-C₆-alkoxy radicals.

The phosphine complexes can be prepared in a manner known per se, for example as described in the documents mentioned at the outset. For example, the starting materials are customary commercially available metal salts such as PdCl₂ or Pd(OCOCH₃)₂, to which the phosphine, eg. P(C₆H₅)₃, P(n—C₄H₉)₃, PCH₃(C₆H₅)₂ or 1,2-bis(diphenylphosphino)ethane, is added.

The amount of phosphine based on the transition metal is usually 0 to 20, in particular 0.1 to 10, mol equivalents, especially preferably 1 to 5 mol equivalents.

The amount of transition metal is not critical. For commercial reasons, one will, of course, rather use a small amount, for example of from 0.1 to 10 mol%, in particular 1 to 5 mol%, based on the starting material II or III.

To prepare the benzoic acids III (T=OH), the reaction is carried out with carbon monoxide and at least equimolar amounts of water based on the starting materials VI. The reactant water can simultaneously also act as the solvent, ie. the maximum amount is not critical.

Depending on the nature of the starting materials and the catalysts used, however, it may also be advantageous to use, as the solvent, an inert solvent which differs from the reactant or the base which is used for the carboxylation reaction.

Inert solvents which are suitable for carboxylation reactions are customary solvents such as hydrocarbons, eg. toluene, xylene, hexane, pentane, cyclohexane, ethers, eg. methyl tert-butyl ether, tetrahydrofuran, dioxane, dimethoxyethane, substituted amides such as dimethylformamide, persubstituted ureas such as tetra-C₁-C₄-alkylureas or nitrites such as benzonitrile or acetonitrile.

In a preferred embodiment of the process, an excess of one of the reactants, in particular the base, is used, thus dispensing with an additional solvent.

The bases which are suitable for the process are all inert bases which are capable of binding the hydrogen iodide or hydrogen bromide which is liberated during the reaction. Examples are tertiary amines such as tert-alkylamines, eg. trialkylamines such as triethylamine, cyclic amines such as N-methylpiperidine or N,N′-dimethylpiperazine, pyridine, alkali metal carbonates or alkali metal hydrogen carbonates, or tetraalkyl-substituted urea derivatives such as tetra-C₁-C₄-alkylurea, eg. tetramethylurea.

The amount of base is not critical; 1 to 10, in particular 1 to 5, mol generally being used. When the base is simultaneously used as the solvent, the amount is generally so chosen that the reactants are dissolved, but unnecessarily high excesses are avoided for practical reasons to save costs, to be able to use small reaction vessels and to guarantee maximum contact between the reactants.

During the reaction, the carbon monoxide pressure is adjusted so that there is always an excess of CO based on VI. The carbon monoxide pressure is preferably from 1 to 250 bar, in particular from 5 to 150 bar, CO at room temperature.

The carbonylation reaction is generally carried out continuously or batchwise at from 20 to 250° C., in particular at from 30 to 150° C. In the case of a batchwise procedure, it is expedient to inject carbon monoxide continuously onto the reaction mixture so as to maintain constant pressure.

Those arylhalogen compounds VII, used as starting compounds, which are not already known can be prepared easily by a suitable combination of known syntheses and in accordance with the above-described reaction sequences.

With a view to the intended use of the pyrazol-4-ylbenzoyl derivatives of the general formula I, the following radicals are suitable as substituents:

L,M hydrogen,

C₁-C₆-alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl or 1-ethyl-2-methylpropyl,

in particular methyl, ethyl, 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl and 1,1-dimethylpropyl;

C₂-C₆-alkenyl such as 2-propenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 3-methyl-2-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-4-butenyl, 3-methyl-3 butenyl [sic], 1,1-dimethyl-2-propenyl,1,2-dimethyl-2-propenyl, 1-ethyl-2-propenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3 pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl and ethyl-2-methyl-2-propenyl,

in particular 1-methyl-2-propenyl, 1-methyl-2-butenyl, 1,1-dimethyl-2-propenyl and 1,1-dimethyl-2-butenyl;

C₂-C₆-alkynyl such as propargyl, 2-butynyl, 3-butenyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 1-methyl-2-butynyl, 1,1-dimethyl-2 propynyl, 1-ethyl-2-propynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 3-methyl-4-pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl and 1-ethyl-1-methyl-2-propynyl;

C₁-C₄-alkoxy such as methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy and 1,1-dimethylethoxy,

in particular C₁-C₃-alkoxy such as methoxy, ethoxy, i-propoxy,

it being possible for these groups to be unsubstituted or substituted by one to five halogen atoms such as fluorine, chlorine, bromine and iodine, preferably fluorine and chlorine, or C₁-C₄-alkoxy as mentioned above.

The group —(A)_(m)—S(O)_(n)R¹ defined above is, for example,

C₁-C₄-alkylthio such as methylthio, ethylthio, n-propylthio, 1-methylethylthio, n-butylthio, 1-methylpropylthio, 2-methylpropylthio and 1,1-dimethylethylthio, in particular methylthio;

C₁-C₄-alkylsulfinyl such as methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, 1-methylethylsulfinyl, n-butylsulfinyl, 1-methylpropylsulfinyl, 2-methylpropylsulfinyl and 1,1-dimethylethylsulfinyl, in particular methylsulfinyl;

C₁-C₄-alkylsulfonyl such as methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, 1-methylethylsulfonyl, n-butylsulfonyl, 1-methylpropylsulfonyl, 2-methylpropylsulfonyl and 1,1-dimethylethylsulfonyl, in particular methylsulfonyl;

C₁-C₄-alkoxysulfonyl such as methoxysulfonyl, ethoxysulfonyl, n-propoxysulfonyl, 1-methylethoxysulfonyl, n-butoxysulfonyl, 1-methylpropoxysulfonyl, 2-methylpropoxysulfonyl and 1,1-dimethylethoxysulfonyl, in particular methoxysulfonyl;

N-C₁-C₄-alkylsulfamoyl such as N-methylsulfamoyl, N-ethylsulfamoyl, N-n-propylsulfamoyl, N-1-methylethylsulfamoyl, N-n-butylsulfamoyl, N-1-methylpropylsulfamoyl, N-2-methylpropylsulfamoyl and N-1,1-dimethylethylsulfamoyl, in particular N-methylsulfamoyl;

N-C₁-C₄-alkylsulfinamoyl such as N-methylsulfinamoyl, N-ethylsulfinamoyl, N-n-propylsulfinamoyl, N-1-methylethylsulfinamoyl, N-n-butylsulfinamoyl, N-1-methylpropylsulfinamoyl, N-2-methylpropylsulfinamoyl and N-1,1-dimethylethylsulfinamoyl, in particular N-methylsulfinamoyl;

di-C₁-C₄-alkylsulfamoyl such as dimethylsulfamoyl, diethylsulfamoyl, dipropylsulfamoyl, dibutylsulfamoyl, N-methyl-N-ethylsulfamoyl, N-methyl-N-propylsulfamoyl, N-methyl-N-1-methylethylsulfamoyl, N-methyl-N-l,1-dimethylethylsulfamoyl, di-1-methylethylsulfamoyl, N-ethyl-N-1-methylethylsulfamoyl and N-ethyl-N-1,1-dimethyl ethylsulfamoyl; in particular dimethylsulfamoyl;

di-C₁-C₄-alkylsulfinamoyl such as dimethylsulfinamoyl, diethylsulfinamoyl, dipropylsulfinamoyl, dibutylsulfinamoyl, N-methyl-N-ethylsulfinamoyl, N-methyl-N-propylsulfinamoyl, N-methyl-N-1-methylethylsulfinamoyl, N-methyl-N-1,1-dimethylethylsulfinamoyl, di-1-methylethylsulfinamoyl, N-ethyl-N-1-methylethylsulfinamoyl and N-ethyl-N-1,1-dimethylethylsulfinamoyl; in particular dimethylsulfinamoyl,

C₁-C₄-alkylsulfinyloxy such as methylsulfinyloxy, ethylsulfinyloxy, n-propylsulfinyloxy, 1-methylethylsulfinyloxy, n-butylsulfinyloxy, 1-methylpropylsulfinyloxy, 2-methylpropylsulfinyloxy and 1,1-dimethylethylsulfinyloxy, in particular methylsulfinyloxy;

C₁-C₄-alkylsulfonyloxy such as methylsulfonyloxy, ethylsulfonyloxy, n-propylsulfonyloxy, 1-methylethylsulfonyloxy, n-butylsulfonyloxy, 1-methylpropylsulfonyloxy, 2-methylpropylsulfonyloxy and 1,1-dimethylethylsulfonyloxy, in particular methylsulfonyloxy;

C₁-C₄-alkylsulfinylamino such as methylsulfinylamino, ethylsulfinylamino, n-propylsulfinylamino, 1-methylethylsulfinylamino, n-butylsulfinylamino, 1-methylpropylsulfinylamino, 2-methylpropylsulfinylamino and 1,1-dimethylethylsulfinylamino, in particular methylsulfinylamino;

C₁-C₄-alkylsulfonylamino such as methylsulfonylamino, ethylsulfonylamino, n-propylsulfonylamino, 1-methylethylsulfonylamino, n-butylsulfonylamino, 1-methylpropylsulfonylamino, 2-methylpropylsulfonylamino and 1,1-dimethylethylsulfonylamino, in particular methylsulfonylamino;

N-C₁-C₄-alkylsulfinyl-N-methylamino such as N-methylsulfinyl-N-methylamino, N-ethylsulfinyl-N-methylamino, N-n-propylsulfinyl-N-methylamino, N-1-methylethylsulfinyl-N-methylamino,

N-n-butylsulfinyl-N-methylamino, N-1-methylpropylsulfinyl-N-methylamino, N-2-methylpropylsulfinyl-N-methylamino and N-1,1-dimethylethylsulfinyl-N-methylamino, in particular N-methylsulfinyl-N-methylamino;

N-C₁-C₄-alkylsulfinyl-N-ethylamino such as N-methylsulfinyl-N-ethylamino, N-ethylsulfinyl-N-ethylaminot N-n-propylsulfinyl-N-ethylamino, N-1-methylethylsulfinyl-N-ethylamino, N-n-butylsulfinyl-N-ethylamino, N-1-methylpropylsulfinyl-N-ethylamino, N-2-methylpropylsulfinyl-N-ethylamino and N-1,1-dimethylethylsulfinyl-N-ethylamino, in particular N-methylsulfinyl-N-ethylamino;

N-C₁-C₄-alkylsulfonyl-N-methylamino such as N-methylsulfonyl-N-methylamino, N-ethylsulfonyl-N-methylamino, N-n-propylsulfonyl-N-methylamino, N-1-methylethylsulfonyl-N-methylamino, N-n-butylsulfonyl-N-methylamino, N-1-methylpropylsulfonyl-N-methylamino, N-2-methylpropylsulfonyl-N-methylamino and N-1,1-dimethylethylsulfonyl-N-methylamino, in particular N-methylsulfonyl-N-methylamino;

N-C₁-C₄-alkylsulfonyl-N-ethylamino such as N-methylsulfonyl-N-ethylamino, N-ethylsulfonyl-N-ethylamino, N-n-propylsulfonyl-N-ethylamino, N-1-methylethylsulfonyl-N-ethylamino, N-n-butylsulfonyl-N-ethylamino, N-1-methylpropylsulfonyl-N-ethylamino, N-2-methylpropylsulfonyl-N-ethylamino and N-1,1-dimethylethylsulfonyl-N-ethylamino, in particular N-methylsulfonyl-N-ethylamino;

C₁-C₄-haloalkylthio such as chloromethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio, chlorodifluoromethylthio, 1-fluoroethylthio, 2-fluoroethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2-chloro-2,2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, 2,2,2-trichloroethylthio and pentafluoroethylthio, in particular trifluoromethylthio.

The group —(A)_(m)—CO—R² defined above is, for example,

C₁-C₄-alkylcarbonyl such as methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, 1-methylethylcarbonyl, n-butylcarbonyl, 1-methylpropylcarbonyl, 2-methylpropylcarbonyl and 1,1-dimethylethylcarbonyl, in particular methylcarbonyl;

C₁-C₄-alkoxycarbonyl such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, 1-methylethoxycarbonyl, n-butoxycarbonyl, 1-methylpropoxycarbonyl, 2-methylpropoxycarbonyl and 1,1-dimethylethoxycarbonyl, in particular methoxycarbonyl;

N-C₁-C₄-alkylcarbamoyl such as N-methylcarbamoyl, N-ethylcarbamoyl, N-n-propylcarbamoyl, N-1-methylethylcarbamoyl, N-n-butylcarbamoyl, N-1-methylpropylcarbamoyl, N-2-methylpropylcarbamoyl and N-1,1-dimethylethylcarbamoyl, in particular N-methylcarbamoyl;

di-C₁-C₄-alkylcarbamoyl such as dimethylcarbamoyl, diethylcarbamoyl, dipropylcarbamoyl, dibutylcarbamoyl, N-methyl-N-ethylcarbamoyl, N-methyl-N-propylcarbamoyl, N-methyl-N-1-methylethylcarbamoyl, N-methyl-N-1,1-dimethylethylcarbamoyl, di-1-methylethylcarbamoyl, N-ethyl-N-1-methylethylcarbamoyl and N-ethyl-N-1,1-dimethylethylcarbamoyl; in particular dimethylcarbamoyl;

C₁-C₄-alkylcarbonyloxy such as methylcarbonyloxy, ethylcarbonyloxy, n-propylcarbonyloxy, 1-methylethylcarbonyloxy, n-butylcarbonyloxy, 1-methylpropylcarbonyloxy, 2-methylpropylcarbonyloxy and 1,1-dimethylethylcarbonyloxy, in particular methylcarbonyloxy;

C₁-C₄-alkylcarbonylamino such as methylcarbonylamino, ethylcarbonylamino, n-propylcarbonylamino, 1-methylethylcarbonylamino, n-butylcarbonylamino, 1-methylpropylcarbonylamino, 2-methylpropylcarbonylamino and 1,1-dimethylethylcarbonylamino, in particular methylcarbonylamino;

N-C₁-C₄-alkylcarbonyl-N-methylamino such as N-methylcarbonyl-N-methylamino, N-ethylcarbonyl-N-methylamino, N-n-propylcarbonyl-N-methylamino, N-1-methylethylcarbonyl-N-methylamino, N-n-butylcarbonyl-N-methylamino, N-1-methylpropylcarbonyl-N-methylamino, N-2-methylpropylcarbonyl-N-methylamino and N-1,1-dimethylethylcarbonyl-N-methylamino, in particular N-methylcarbonyl-N-methylamino.

X is, for example,

CH₂, CH(CH₃), C((CH₃)₂), CH(C₂H₅), C((C₂H₅)₂), CH(C₆H₅), CH₂—CH₂, CH₂—CH(CH₃), CH₂—C((CH₃)₂), CH(CH₃)—CH(CH₃), CH(CH₃)—C((CH₃)₂), C((CH₃)₂)—C((CH₃)₂), CH₂—CH(C₂H₅), CH₂—C((C₂H₅)₂), CH(C₂H₅)—CH(C₂H₅), CH(C₂H₅)—C((C₂H₅)₂), C((C₂H₅)₂)—C((C₂H₅)₂), CH₂—CH(C₃H₇), CH₂—CH(iC₃H₇), CH₂—CH(C₄H₉), CH₂—CH(iC₄H₉), CH₂—CH(Br), CH₂—C((Br)₂), CH(Br)—CH(Br), C((Br)₂)—C((Br)₂), CH₂—CH(Cl), CH₂—C((Cl)₂), CH(Cl)—C((Cl₂), C((Cl)₂)—C((Cl)₂), CH₂—CH(C₆H₅), CH(C₆H₅)—CH(C₆H₅), CH₂—CH(p—NO₂C₆H₅), CH═CH, C(CH₃)═CH, C(CH₃)═CCH₃, CH═CBr, CH═CCl, CBr═CBr, CCl═CCl, CH═C(OCH₃), CH═C(C₆H₅), C(C₆H₅)═C(C₆H₅), C(C₂H₅)═CH, C(C₂H₅)═C(C₂H₅), CH═C(C₃H₅), CH═C(C₄H₇), CH₂—CH═CH, CH(CH₃)—CH═CH, C((CH₃)₂)—CH═CH, CH₂—CH═C(CH₃), CH₂—C(CH₃)═CH, CH₂—C(CH₃)═C(CH₃), CH(CH₃)—C(CH₃)═C(CH₃), C((CH₃)₂)—C(CH₃)═C(CH₃), N—H, N—CH₃, N—C₂H₅, N—C₃H₇, N—C₄H₉, N—iCH₃H₇, N—OCH₃, N—OC₂H₅, N—CH₂C₆H₅, N—C₂H₅,

Y is, for example,

C═O, CH—OH, CH—OCH₃, CH—OC₂H₅, CH—OC₃H₇, CH—OiPr, CH—OC₄H₉, CH—OiBu, CH—OC₅H₁₁, CH—OC₆H₁₃, CH—OC₆H₅, C(CH₃)—OCH₃, C(CH₃)—OC₂H₅, C(CH₃)—OC₃H₇, C(CH₃)—OC₄H₉, C(CH₃)-OiPr, C(CH₃)—OiBu, C(CH₃)—OtBu, C(CH₃)—OPh, CH₂, CH(CH₃), C((CH₃)₂), C═N—CH₃, C═N—C₂H₅, C═N—C₃H₇, CN═C₄H₉, C═N—iC₄H₉, C═N—tC₄H₉, C═N—iPr, C═N—OCH₃, C═N—OC₂H₅, C═N—OC₃H₇, C═N—OC₄H₉, C═N—OiC₄H₉, C═N—OtC₄H₉, C═N—OCH₂CH═CH₂, C═N—OCH(CH₃)CH═CH₂, C═N—OCH₂CH═CHCH₃, C═N—OCH₂CH═C(CH₃)₂, C═N—OCH₂CH═CHBr, C═N—OCH₂CH═CHCl, C═N—OCH₂CH═CHC₂H₅, C═N—OCH₂C≡CH, C═N—OCH₂C≡CCH3, C═N—OCH₂C₆H₅, CH—NH(OCH₃), CH—NH(OC₂H₅), CH—NH(OiPr), CH—NH(OnPr), CH—NH(OC₆H₅), CH—NCH₃(OCH₃), CH—NCH₃(OC₂H₅), CH—NCH₃(OiPr), CH—NCH₃(OnPr), CH—NCH₃(OC₆H₅), CH—NH(CH₃), CH—NH(C₂H₅), CH—NH(C₃H₇), CH—NH(C₄H₉), CH—NH(iPr), CH—NH(iBu), CH—NH(tBu), CH—NH(C₆H₅), CH—N(CH₃)₂, CH—NCH₃(C₂H₅), CH—NCH₃(C₃H₇), CH—NCH₃(C₄H₉), CH—NCH₃(iPr), CH—NCH₃(iBu), C═N—NH₂, C═N—NHCH₃, C═N—N((CH₃)₂), C═N—NH(C₂H₅), C═N—NCH₃(C₂H₅), C═N—N((C₂H₅)₂), CH—SCH₃, CH—SC₂H₅, CH—SC₃H₇, CH—SC₄H₉, CH—SPr, CH—SiBu, CH—SH, C(CH₃)—SCH₃, C(CH₃)—SC₂H₅, C(CH₃)—SC₃H₇, 1,3-dioxanyl, 1,3-dioxolanyl, 5,5-dimethyl-1,3-dioxanyl.

Preferred pyrazol-4-ylbenzoyl derivatives are those of the formula Ia

where L is hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, C₁-C₄-haloalkylthio, C₁-C₄-alkylsulfonyl, halogen, nitro or cyano and M is hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkylthio, C₁-C₄-alkylsulfonyl, halogen, nitro or cyano and Q, X, n and Y have the abovementioned meanings, where, in the event that Y=C=O, X is other than NR²³.

Furthermore preferred pyrazol-4-ylbenzoyl derivatives are those of the formula Ib

where L is C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, halogen, nitro or cyano and M is hydrogen C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, halogen, nitro or cyano and Q, X, n and Y have the abovementioned meanings, where, in the event that Y=C=O, X is other than NR²³.

Further preferred pyrazol-4-ylbenzoyl derivatives of the formula I are those where the radicals L and M are hydrogen, methyl, methoxy, chlorine, cyano, nitro or trifluoromethyl.

Preferred pyrazol-4-ylbenzoyl derivatives are those of the formula Ic

where L is hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, halogen, nitro or cyano and M is hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, halogen, nitro or cyano and Q, n, Y and R²², R²¹, R¹² and R¹³ have the abovementioned meanings.

Also preferred pyrazol-4-ylbenzoyl derivatives are those of the formula Id

where L is hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, halogen, nitro or cyano and M is hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, halogen, nitro or cyano and Q, n, Y and R¹² and R¹³ have the abovementioned meanings.

Other preferred pyrazol-4-ylbenzoyl derivatives are those of the formula Ie

where L is hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, halogen, nitro or cyano and M is hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, halogen, nitro or cyano and Q, n, Y and R¹² and R¹³ have the abovementioned meanings.

Other preferred pyrazol-4-ylbenzoyl derivatives of the formula I are those where n is one or two and Y is CR^(7—OR) ⁸, where R⁷ and R⁸ have the abovementioned meanings.

TABLE 1 Compounds of the formula

No. R¹⁵ R¹⁶ R¹⁷ n X Y L M 1.1 CH₃ CH₃ H 0 CH₂ C═O H H 1.2 CH₃ CH₃ H 2 CH₂ C═O H H 1.3 CH₃ CH₃ H 0 CH₂ CHOCH₃ H H 1.4 CH₃ CH₃ H 2 CH₂ CHOCH₃ H H 1.5 CH₃ CH₃ H 0 CH₂ CHOC₂H₅ H H 1.6 CH₃ CH₃ H 2 CH₂ CHOC₂H₅ H H 1.7 CH₃ CH₃ H 0 CH₂ CHOiPr H H 1.8 CH₃ CH₃ H 2 CH₂ CHOiPr H H 1.9 CH₃ CH₃ H 0 CH₂ CHOH H H 1.10 CH₃ CH₃ H 2 CH₂ CHOH H H 1.11 CH₃ CH₃ H 0 CH₂ C═NOCH₃ H H 1.12 CH₃ CH₃ H 2 CH₂ C═NOCH₃ H H 1.13 CH₃ CH₃ H 0 CH₂ C═NOC₂H₅ H H 1.14 CH₃ CH₃ H 2 CH₂ C═NOC₂H₅ H H 1.15 CH₃ CH₃ H 0 CH₂ C═NOiPr H H 1.16 CH₃ CH₃ H 2 CH₂ C═NOiPr H H 1.17 CH₃ CH₃ H 0 CH₂ C═NOCH₂CH═CHCl H H 1.18 CH₃ CH₃ H 2 CH₂ C═NOCH₂CH═CHCl H H 1.19 CH₃ CH₃ H 0 CH₂ C═NOCH₂C₆H₅ H H 1.20 CH₃ CH₃ H 2 CH₂ C═NOCH₂C₆H₅ H H 1.21 CH₃ CH₃ H 0 CH₂ C(CH₃)₂ H H 1.22 CH₃ CH₃ H 2 CH₂ C(CH₃)₂ H H 1.23 C₂H₅ H H 0 CH₂ C═O H H 1.24 C₂H₅ H H 2 CH₂ C═O H H 1.25 C₂H₅ H H 0 CH₂ CHOCH₃ H H 1.26 C₂H₅ H H 2 CH₂ CHOCH₃ H H 1.27 C₂H₅ H H 0 CH₂ CHOC₂H₅ H H 1.28 C₂H₅ H H 2 CH₂ CHOC₂H₅ H H 1.29 C₂H₅ H H 0 CH₂ CHOiPr H H 1.30 C₂H₅ H H 2 CH₂ CHOiPr H H 1.31 C₂H₅ H H 0 CH₂ CHOH H H 1.32 C₂H₅ H H 2 CH₂ CHOH H H 1.33 C₂H₅ H H 0 CH₂ C═NOCH₃ H H 1.34 C₂H₅ H H 2 CH₂ C═NOCH₃ H H 1.35 C₂H₅ H H 0 CH₂ C═NOC₂H₅ H H 1.36 C₂H₅ H H 2 CH₂ C═NOC₂H₅ H H 1.37 C₂H₅ H H 0 CH₂ C═NOiPr H H 1.38 C₂H₅ H H 2 CH₂ C═NOiPr H H 1.39 C₂H₅ H H 0 CH₂ C═NOCH₂CH═CHCl H H 1.40 C₂H₅ H H 2 CH₂ C═NOCH₂CH═CHCl H H 1.41 C₂H₅ H H 0 CH₂ C═NOCH₂C₆H₅ H H 1.42 C₂H₅ H H 2 CH₂ C═NOCH₂C₆H₅ H H 1.43 C₂H₅ H H 0 CH₂ C(CH₃)₂ H H 1.44 C₂H₅ H H 2 CH₂ C(CH₃)₂ H H 1.45 CH₃ CH₃ H 0 CH₂ C═O H CH₃ 1.46 CH₃ CH₃ H 2 CH₂ C═O H CH₃ 1.47 CH₃ CH₃ H 0 CH₂ CHOCH₃ H CH₃ 1.48 CH₃ CH₃ H 2 CH₂ CHOCH₃ H CH₃ 1.49 CH₃ CH₃ H 0 CH₂ CHOC₂H₅ H CH₃ 1.50 CH₃ CH₃ H 2 CH₂ CHOC₂H₅ H CH₃ 1.51 CH₃ CH₃ H 0 CH₂ CHOiPr H CH₃ 1.52 CH₃ CH₃ H 2 CH₂ CHOiPr H CH₃ 1.53 CH₃ CH₃ H 0 CH₂ CHOH H CH₃ 1.54 CH₃ CH₃ H 2 CH₂ CHOH H CH₃ 1.55 CH₃ CH₃ H 0 CH₂ C═NOCH₃ H CH₃ 1.56 CH₃ CH₃ H 2 CH₂ C═NOCH₃ H CH₃ 1.57 CH₃ CH₃ H 0 CH₂ C═NOC₂H₅ H CH₃ 1.58 CH₃ CH₃ H 2 CH₂ C═NOC₂H₅ H CH₃ 1.59 CH₃ CH₃ H 0 CH₂ C═NOiPr H CH₃ 1.60 CH₃ CH₃ H 2 CH₂ C═NOiPr H CH₃ 1.61 CH₃ CH₃ H 0 CH₂ C═NOCH₂CH═CHCl H CH₃ 1.62 CH₃ CH₃ H 2 CH₂ C═NOCH₂CH═CHCl H CH₃ 1.63 CH₃ CH₃ H 0 CH₂ C═NOCH₂C₆H₅ H CH₃ 1.64 CH₃ CH₃ H 2 CH₂ C═NOCH₂C₆H₅ H CH₃ 1.65 CH₃ CH₃ H 0 CH₂ C(CH₃)₂ H CH₃ 1.66 CH₃ CH₃ H 2 CH₂ C(CH₃)₂ H CH₃ 1.67 C₂H₅ H H 0 CH₂ C═O H CH₃ 1.68 C₂H₅ H H 2 CH₂ C═O H CH₃ 1.69 C₂H₅ H H 0 CH₂ CHOCH₃ H CH₃ 1.70 C₂H₅ H H 2 CH₂ CHOCH₃ H CH₃ 1.71 C₂H₅ H H 0 CH₂ CHOC₂H₅ H CH₃ 1.72 C₂H₅ H H 2 CH₂ CHOC₂H₅ H CH₃ 1.73 C₂H₅ H H 0 CH₂ CHOiPr H CH₃ 1.74 C₂H₅ H H 2 CH₂ CHOiPr H CH₃ 1.75 C₂H₅ H H 0 CH₂ CHOH H CH₃ 1.76 C₂H₅ H H 2 CH₂ CHOH H CH₃ 1.77 C₂H₅ H H 0 CH₂ C═NOCH₃ H CH₃ 1.78 C₂H₅ H H 2 CH₂ C═NOCH₃ H CH₃ 1.79 C₂H₅ H H 0 CH₂ C═NOC₂H₅ H CH₃ 1.80 C₂H₅ H H 2 CH₂ C═NOC₂H₅ H CH₃ 1.81 C₂H₅ H H 0 CH₂ C═NOiPr H CH₃ 1.82 C₂H₅ H H 2 CH₂ C═NOiPr H CH₃ 1.83 C₂H₅ H H 0 CH₂ C═NOCH₂CH═CHCl H CH₃ 1.84 C₂H₅ H H 2 CH₂ C═NOCH₂CH═CHCl H CH₃ 1.85 C₂H₅ H H 0 CH₂ C═NOCH₂C₆H₅ H CH₃ 1.86 C₂H₅ H H 2 CH₂ C═NOCH₂C₆H₅ H CH₃ 1.87 C₂H₅ H H 0 CH₂ C(CH₃)₂ H CH₃ 1.88 C₂H₅ H H 2 CH₂ C(CH₃)₂ H CH₃ 1.89 CH₃ CH₃ H 0 CH₂ C═O H Cl 1.90 CH₃ CH₃ H 2 CH₂ C═O H C1 1.91 CH₃ CH₃ H 0 CH₂ CHOCH₃ H Cl 1.92 CH₃ CH₃ H 2 CH₂ CHOCH₃ H Cl 1.93 CH₃ CH₃ H 0 CH₂ CHOC₂H₅ H Cl 1.94 CH₃ CH₃ H 2 CH₂ CHOC₂H₅ H Cl 1.95 CH₃ CH₃ H 0 CH₂ CHOiPr H Cl 1.96 CH₃ CH₃ H 2 CH₂ CHOiPr H Cl 1.97 CH₃ CH₃ H 0 CH₂ CHOH H Cl 1.98 CH₃ CH₃ H 2 CH₂ CHOH H Cl 1.99 CH₃ CH₃ H 0 CH₂ C═NOCH₃ H Cl 1.100 CH₃ CH₃ H 2 CH₂ C═NOCH₃ H Cl 1.101 CH₃ CH₃ H 0 CH₂ C═NOC₂H₅ H Cl 1.102 CH₃ CH₃ H 2 CH₂ C═NOC₂H₅ H Cl 1.103 CH₃ CH₃ H 0 CH₂ C═NOiPr H Cl 1.104 CH₃ CH₃ H 2 CH₂ C═NOiPr H Cl 1.105 CH₃ CH₃ H 0 CH₂ C═NOCH₂CH═CHCl H Cl 1.106 CH₃ CH₃ H 2 CH₂ C═NOCH₂CH═CHCl H Cl 1.107 CH₃ CH₃ H 0 CH₂ C═NOCH₂C₆H₅ H Cl 1.108 CH₃ CH₃ H 2 CH₂ C═NOCH₂C₆H₅ H Cl 1.109 CH₃ CH₃ H 0 CH₂ C(CH₃)₂ H Cl 1.110 CH₃ CH₃ H 2 CH₂ C(CH₃)₂ H Cl 1.111 C₂H₅ H H 0 CH₂ C═O H Cl 1.112 C₂H₅ H H 2 CH₂ C═O H Cl 1.113 C₂H₅ H H 0 CH₂ CHOCH₃ H Cl 1.114 C₂H₅ H H 2 CH₂ CHOCH₃ H Cl 1.115 C₂H₅ H H 0 CH₂ CHOC₂H₅ H Cl 1.116 C₂H₅ H H 2 CH₂ CHOC₂H₅ H Cl 1.117 C₂H₅ H H 0 CH₂ CHOiPr H Cl 1.118 C₂H₅ H H 2 CH₂ CHOiPr H Cl 1.119 C₂H₅ H H 0 CH₂ CHOH H Cl 1.120 C₂H₅ H H 2 CH₂ CHOH H Cl 1.121 C₂H₅ H H 0 CH₂ C═NOCH₃ H Cl 1.122 C₂H₅ H H 2 CH₂ C═NOCH₃ H Cl 1.123 C₂H₅ H H 0 CH₂ C═NOC₂H₅ H Cl 1.124 C₂H₅ H H 2 CH₂ C═NOC₂H₅ H Cl 1.125 C₂H₅ H H 0 CH₂ C═NOiPr H Cl 1.126 C₂H₅ H H 2 CH₂ C═NOiPr H Cl 1.127 C₂H₅ H H 0 CH₂ C═NOCH₂CH═CHCl H Cl 1.128 C₂H₅ H H 2 CH₂ C═NOCH₂CH═CHCl H Cl 1.129 C₂H₅ H H 0 CH₂ C═NOCH₂C₆H₅ H Cl 1.130 C₂H₅ H H 2 CH₂ C═NOCH₂C₆H₅ H Cl 1.131 C₂H₅ H H 0 CH₂ C(CH₃)₂ H Cl 1.132 C₂H₅ H H 2 CH₂ C(CH₃)₂ H Cl 1.133 CH₃ CH₃ H 0 (CH₂)₂ C═O H Cl 1.134 CH₃ CH₃ H 2 (CH₂)₂ C═O H Cl 1.135 CH₃ CH₃ H 0 (CH₂)₂ CHOCH₃ H Cl 1.136 CH₃ CH₃ H 2 (CH₂)₂ CHOCH₃ H Cl 1.137 CH₃ CH₃ H 0 (CH₂)₂ CHOC₂H₅ H Cl 1.138 CH₃ CH₃ H 2 (CH₂)₂ CHOC₂H₅ H Cl 1.139 CH₃ CH₃ H 0 (CH₂)₂ CHOiPr H Cl 1.140 CH₃ CH₃ H 2 (CH₂)₂ CHOiPr H Cl 1.141 CH₃ CH₃ H 0 (CH₂)₂ CHOH H Cl 1.142 CH₃ CH₃ H 2 (CH₂)₂ CHOH H Cl 1.143 CH₃ CH₃ H 0 (CH₂)₂ C═NOCH₃ H Cl 1.144 CH₃ CH₃ H 2 (CH₂)₂ C═NOCH₃ H Cl 1.145 CH₃ CH₃ H 0 (CH₂)₂ C═NOC₂H₅ H Cl 1.146 CH₃ CH₃ H 2 (CH₂)₂ C═NOC₂H₅ H Cl 1.147 CH₃ CH₃ H 0 (CH₂)₂ C═NOiPr H Cl 1.148 CH₃ CH₃ H 2 (CH₂)₂ C═NOiPr H Cl 1.149 CH₃ CH₃ H 0 (CH₂)₂ C═NOCH₂CH═CHCl H Cl 1.150 CH₃ CH₃ H 2 (CH₂)₂ C═NOCH₂CH═CHCl H Cl 1.151 CH₃ CH₃ H 0 (CH₂)₂ C═NOCH₂C₆H₅ H Cl 1.152 CH₃ CH₃ H 2 (CH₂)₂ C═NOCH₂C₆H₅ H Cl 1.153 CH₃ CH₃ H 0 (CH₂)₂ C(CH₃)₂ H Cl 1.154 CH₃ CH₃ H 2 (CH₂)₂ C(CH₃)₂ H Cl 1.155 C₂H₅ H H 0 (CH₂)₂ C═O H Cl 1.156 C₂H₅ H H 2 (CH₂)₂ C═O H Cl 1.157 C₂H₅ H H 0 (CH₂)₂ CHOCH₃ H Cl 1.158 C₂H₅ H H 2 (CH₂)₂ CHOCH₃ H Cl 1.159 C₂H₅ H H 0 (CH₂)₂ CHOC₂H₅ H Cl 1.160 C₂H₅ H H 2 (CH₂)₂ CHOC₂H₅ H Cl 1.161 C₂H₅ H H 0 (CH₂)₂ CHOiPr H Cl 1.162 C₂H₅ H H 2 (CH₂)₂ CHOiPr H Cl 1.163 C₂H₅ H H 0 (CH₂)₂ CHOH H Cl 1.164 C₂H₅ H H 2 (CH₂)₂ CHOH H Cl 1.165 C₂H₅ H H 0 (CH₂)₂ C═NOCH₃ H Cl 1.166 C₂H₅ H H 2 (CH₂)₂ C═NOCH₃ H Cl 1.167 C₂H₅ H H 0 (CH₂)₂ C═NOC₂H₅ H Cl 1.168 C₂H₅ H H 2 (CH₂)₂ C═NOC₂H₅ H Cl 1.169 C₂H₅ H H 0 (CH₂)₂ C═NOiPr H Cl 1.170 C₂H₅ H H 2 (CH₂)₂ C═NOiPr H Cl 1.171 C₂H₅ H H 0 (CH₂)₂ C═NOCH₂CH═CHCl H Cl 1.172 C₂H₅ H H 2 (CH₂)₂ C═NOCH₂CH═CHCl H Cl 1.173 C₂H₅ H H 0 (CH₂)₂ C═NOCH₂C₆H₅ H Cl 1.174 C₂H₅ H H 2 (CH₂)₂ C═NOCH₂C₆H₅ H Cl 1.175 C₂H₅ H H 0 (CH₂)₂ C(CH₃)₂ H Cl 1.176 C₂H₅ H H 2 (CH₂)₂ C(CH₃)₂ H Cl 1.177 CH₃ CH₃ H 0 (CH₂)₂ C═O H CH₃ 1.178 CH₃ CH₃ H 2 (CH₂)₂ C═O H CH₃ 1.179 CH₃ CH₃ H 0 (CH₂)₂ CHOCH₃ H CH₃ 1.180 CH₃ CH₃ H 2 (CH₂)₂ CHOCH₃ H CH₃ 1.181 CH₃ CH₃ H 0 (CH₂)₂ CHOC₂H₅ H CH₃ 1.182 CH₃ CH₃ H 2 (CH₂)₂ CHOC₂H₅ H CH₃ 1.183 CH₃ CH₃ H 0 (CH₂)₂ CHOiPr H CH₃ 1.184 CH₃ CH₃ H 2 (CH₂)₂ CHOiPr H CH₃ 1.185 CH₃ CH₃ H 0 (CH₂)₂ CHOH H CH₃ 1.186 CH₃ CH₃ H 2 (CH₂)₂ CHOH H CH₃ 1.187 CH₃ CH₃ H 0 (CH₂)₂ C═NOCH₃ H CH₃ 1.188 CH₃ CH₃ H 2 (CH₂)₂ C═NOCH₃ H CH₃ 1.189 CH₃ CH₃ H 0 (CH₂)₂ C═NOC₂H₅ H CH₃ 1.190 CH₃ CH₃ H 2 (CH₂)₂ C═NOC₂H₅ H CH₃ 1.191 CH₃ CH₃ H 0 (CH₂)₂ C═NOiPr H CH₃ 1.192 CH₃ CH₃ H 2 (CH₂)₂ C═NOiPr H CH₃ 1.193 CH₃ CH₃ H 0 (CH₂)₂ C═NOCH₂CH═CHCl H CH₃ 1.194 CH₃ CH₃ H 2 (CH₂)₂ C═NOCH₂CH═CHCl H CH₃ 1.195 CH₃ CH₃ H 0 (CH₂)₂ C═NOCH₂C₆H₅ H CH₃ 1.196 CH₃ CH₃ H 2 (CH₂)₂ C═NOCH₂C₆H₅ H CH₃ 1.197 CH₃ CH₃ H 0 (CH₂)₂ C(CH₃)₂ H CH₃ 1.198 CH₃ CH₃ H 2 (CH₂)₂ C(CH₃)₂ H CH₃ 1.199 C₂H₅ H H 0 (CH₂)₂ C═O H CH₃ 1.200 C₂H₅ H H 2 (CH₂)₂ C═O H CH₃ 1.201 C₂H₅ H H 0 (CH₂)₂ CHOCH₃ H CH₃ 1.202 C₂H₅ H H 2 (CH₂)₂ CHOCH₃ H CH₃ 1.203 C₂H₅ H H 0 (CH₂)₂ CHOC₂H₅ H CH₃ 1.204 C₂H₅ H H 2 (CH₂)₂ CHOC₂H₅ H CH₃ 1.205 C₂H₅ H H 0 (CH₂)₂ CHOiPr H CH₃ 1.206 C₂H₅ H H 2 (CH₂)₂ CHOiPr H CH₃ 1.207 C₂H₅ H H 0 (CH₂)₂ CHOH H CH₃ 1.208 C₂H₅ H H 2 (CH₂)₂ CHOH H CH₃ 1.209 C₂H₅ H H 0 (CH₂)₂ C═NOCH₃ H CH₃ 1.210 C₂H₅ H H 2 (CH₂)₂ C═NOCH₃ H CH₃ 1.211 C₂H₅ H H 0 (CH₂)₂ C═NOC₂H₅ H CH₃ 1.212 C₂H₅ H H 2 (CH₂)₂ C═NOC₂H₅ H CH₃ 1.213 C₂H₅ H H 0 (CH₂)₂ C═NOiPr H CH₃ 1.214 C₂H₅ H H 2 (CH₂)₂ C═NOiPr H CH₃ 1.215 C₂H₅ H H 0 (CH₂)₂ C═NOCH₂CH═CHCl H CH₃ 1.216 C₂H₅ H H 2 (CH₂)₂ C═NOCH₂CH═CHCl H CH₃ 1.217 C₂H₅ H H 0 (CH₂)₂ C═NOCH₂C₆H₅ H CH₃ 1.218 C₂H₅ H H 2 (CH₂)₂ C═NOCH₂C₆H₅ H CH₃ 1.219 C₂H₅ H H 0 (CH₂)₂ C(CH₃)₂ H CH₃ 1.220 C₂H₅ H H 2 (CH₂)₂ C(CH₃)₂ H CH₃ 1.221 CH₃ CH₃ p-CH₃—C₆H₄—SO₂— 0 (CH₂)₂ C═O H CH₃ 1.222 CH₃ CH₃ p-CH₃—C₆H₄—SO₂— 2 (CH₂)₂ C═O H CH₃ 1.223 CH₃ CH₃ p-CH₃—C₆H₄—SO₂— 0 (CH₂)₂ CHOCH₃ H CH₃ 1.224 CH₃ CH₃ p-CH₃—C₆H₄—SO₂— 2 (CH₂)₂ CHOCH₃ H CH₃ 1.225 CH₃ CH₃ p-CH₃—C₆H₄—SO₂— 0 (CH₂)₂ CHOC₂H₅ H CH₃ 1.226 CH₃ CH₃ p-CH₃—C₆H₄—SO₂— 2 (CH₂)₂ CHOC₂H₅ H CH₃ 1.227 CH₃ CH₃ p-CH₃—C₆H₄—SO₂— 0 (CH₂)₂ CHOiPr H CH₃ 1.228 CH₃ CH₃ p-CH₃—C₆H₄—SO₂— 2 (CH₂)₂ CHOiPr H CH₃ 1.229 CH₃ CH₃ p-CH₃—C₆H₄—SO₂— 0 (CH₂)₂ CHOH H CH₃ 1.230 CH₃ CH₃ p-CH₃—C₆H₄—SO₂— 2 (CH₂)₂ CHOH H CH₃ 1.231 CH₃ CH₃ p-CH₃—C₆H₄—SO₂— 0 (CH₂)₂ C═NOCH₃ H CH₃ 1.232 CH₃ CH₃ p-CH₃—C₆H₄—SO₂— 2 (CH₂)₂ C═NOCH₃ H CH₃ 1.233 CH₃ CH₃ p-CH₃—C₆H₄—SO₂— 0 (CH₂)₂ C═NOC₂H₅ H CH₃ 1.234 CH₃ CH₃ p-CH₃—C₆H₄—SO₂— 2 (CH₂)₂ C═NOC₂H₅ H CH₃ 1.235 CH₃ CH₃ p-CH₃—C₆H₄—SO₂— 0 (CH₂)₂ C═NOiPr H CH₃ 1.236 CH₃ CH₃ p-CH₃—C₆H₄—SO₂— 2 (CH₂)₂ C═NOiPr H CH₃ 1.237 CH₃ CH₃ p-CH₃—C₆H₄—SO₂— 0 (CH₂)₂ C═NOCH₂CH═CHCl H CH₃ 1.238 CH₃ CH₃ p-CH₃—C₆H₄—SO₂— 2 (CH₂)₂ C═NOCH₂CH═CHCl H CH₃ 1.239 CH₃ CH₃ p-CH₃—C₆H₄—SO₂— 0 (CH₂)₂ C═NOCH₂C₆H₅ H CH₃ 1.240 CH₃ CH₃ p-CH₃—C₆H₄—SO₂— 2 (CH₂)₂ C═NOCH₂C₆H₅ H CH₃ 1.241 CH₃ CH₃ p-CH₃—C₆H₄—SO₂— 0 (CH₂)₂ C(CH₃)₂ H CH₃ 1.242 CH₃ CH₃ p-CH₃—C₆H₄—SO₂— 2 (CH₂)₂ C(CH₃)₂ H CH₃ 1.243 C₂H₅ H p-CH₃—C₆H₄—SO₂— 0 (CH₂)₂ C═O H CH₃ 1.244 C₂H₅ H p-CH₃—C₆H₄—SO₂— 2 (CH₂)₂ C═O H CH₃ 1.245 C₂H₅ H p-CH₃—C₆H₄—SO₂— 0 (CH₂)₂ CHOCH₃ H CH₃ 1.246 C₂H₅ H p-CH₃—C₆H₄—SO₂— 2 (CH₂)₂ CHOCH₃ H CH₃ 1.247 C₂H₅ H p-CH₃—C₆H₄—SO₂— 0 (CH₂)₂ CHOC₂H₅ H CH₃ 1.248 C₂H₅ H p-CH₃—C₆H₄—SO₂— 2 (CH₂)₂ CHOC₂H₅ H CH₃ 1.249 C₂H₅ H p-CH₃—C₆H₄—SO₂— 0 (CH₂)₂ CHOiPr H CH₃ 1.250 C₂H₅ H p-CH₃—C₆H₄—SO₂— 2 (CH₂)₂ CHOiPr H CH₃ 1.251 C₂H₅ H p-CH₃—C₆H₄—SO₂— 0 (CH₂)₂ CHOH H CH₃ 1.252 C₂H₅ H p-CH₃—C₆H₄—SO₂— 2 (CH₂)₂ CHOH H CH₃ 1.253 C₂H₅ H p-CH₃—C₆H₄—SO₂— 0 (CH₂)₂ C═NOCH₃ H CH₃ 1.254 C₂H₅ H p-CH₃—C₆H₄—SO₂— 2 (CH₂)₂ C═NOCH₃ H CH₃ 1.255 C₂H₅ H p-CH₃—C₆H₄—SO₂— 0 (CH₂)₂ C═NOC₂H₅ H CH₃ 1.256 C₂H₅ H p-CH₃—C₆H₄—SO₂— 2 (CH₂)₂ C═NOC₂H₅ H CH₃ 1.257 C₂H₅ H p-CH₃—C₆H₄—SO₂— 0 (CH₂)₂ C═NOiPr H CH₃ 1.258 C₂H₅ H p-CH₃—C₆H₄—SO₂— 2 (CH₂)₂ C═NOiPr H CH₃ 1.259 C₂H₅ H p-CH₃—C₆H₄—SO₂— 0 (CH₂)₂ C═NOCH₂CH═CHCl H CH₃ 1.260 C₂H₅ H p-CH₃—C₆H₄—SO₂— 2 (CH₂)₂ C═NOCH₂CH═CHCl H CH₃ 1.261 C₂H₅ H p-CH₃—C₆H₄—SO₂— 0 (CH₂)₂ C═NOCH₂C₆H₅ H CH₃ 1.262 C₂H₅ H p-CH₃—C₆H₄—SO₂— 2 (CH₂)₂ C═NOCH₂C₆H₅ H CH₃ 1.263 C₂H₅ H p-CH₃—C₆H₄—SO₂— 0 (CH₂)₂ C(CH₃)₂ H CH₃ 1.264 C₂H₅ H p-CH₃—C₆H₄—SO₂— 2 (CH₂)₂ C(CH₃)₂ H CH₃ 1.265 CH₃ CH₃ H 0 CH₂ CH—NHCH₃ H H 1.266 CH₃ CH₃ H 2 CH₂ CH—NHCH₃ H H 1.267 CH₃ CH₃ H 0 CH₂ CH—NHC₂H₅ H H 1.268 CH₃ CH₃ H 2 CH₂ CH—NHC₂H₅ H H 1.269 CH₃ CH₃ H 0 CH₂ CH—N(CH₃)₂ H H 1.270 CH₃ CH₃ H 2 CH₂ CH—N(CH₃)₂ H H 1.271 CH₃ CH₃ H 0 CH₂ CH—NHOC₂H₅ H H 1.272 CH₃ CH₃ H 2 CH₂ CH—NHOC₂H₅ H H 1.273 CH₃ CH₃ H 0 CH₂ CH—N(CH₃)OC₂H₅ H H 1.274 CH₃ CH₃ H 2 CH₂ CH—N(CH₃)OC₂H₅ H H 1.275 CH₃ CH₃ H 0 CH₂ C═N—NH₂ H H 1.276 CH₃ CH₃ H 2 CH₂ C═N—NH₂ H H 1.277 CH₃ CH₃ H 0 CH₂ C═N—N(CH₃)₂ H H 1.278 CH₃ CH₃ H 2 CH₂ C═N—N(CH₃)₂ H H 1.279 CH₃ CH₃ H 0 CH₂ C(CH₃)—OCH₃ H H 1.280 CH₃ CH₃ H 2 CH₂ C(CH₃)—OCH₃ H H 1.281 CH₃ CH₃ H 0 CH₂ O H H 1.282 CH₃ CH₃ H 2 CH₂ O H H 1.283 C₂H₅ H H 0 CH₂ CH—NHCH₃ H H 1.284 C₂H₅ H H 2 CH₂ CH—NHCH₃ H H 1.285 C₂H₅ H H 0 CH₂ CH—NHC₂H₅ H H 1.286 C₂H₅ H H 2 CH₂ CH—NHC₂H₅ H H 1.287 C₂H₅ H H 0 CH₂ CH—N(CH₃)₂ H H 1.288 C₂H₅ H H 2 CH₂ CH—N(CH₃)₂ H H 1.289 C₂H₅ H H 0 CH₂ CH—NHOC₂H₅ H H 1.290 C₂H₅ H H 2 CH₂ CH—NHOC₂H₅ H H 1.291 C₂H₅ H H 0 CH₂ CH—N(CH₃)OC₂H₅ H H 1.292 C₂H₅ H H 2 CH₂ CH—N(CH₃)OC₂H₅ H H 1.293 C₂H₅ H H 0 CH₂ C═N—NH₂ H H 1.294 C₂H₅ H H 2 CH₂ C═N—NH₂ H H 1.295 C₂H₅ H H 0 CH₂ C═N—N(CH₃)₂ H H 1.296 C₂H₅ H H 2 CH₂ C═N—N(CH₃)₂ H H 1.297 C₂H₅ H H 0 CH₂ C(CH₃)—OCH₃ H H 1.298 C₂H₅ H H 2 CH₂ C(CH₃)—OCH₃ H H 1.299 C₂H₅ H H 0 CH₂ O H H 1.300 C₂H₅ H H 2 CH₂ O H H 1.301 CH₃ CH₃ H 0 CH₂ CH—NHCH₃ H CH₃ 1.302 CH₃ CH₃ H 2 CH₂ CH—NHCH₃ H CH₃ 1.303 CH₃ CH₃ H 0 CH₂ CH—NHC₂H₅ H CH₃ 1.304 CH₃ CH₃ H 2 CH₂ CH—NHC₂H₅ H CH₃ 1.305 CH₃ CH₃ H 0 CH₂ CH—N(CH₃)₂ H CH₃ 1.306 CH₃ CH₃ H 2 CH₂ CH—N(CH₃)₂ H CH₃ 1.307 CH₃ CH₃ H 0 CH₂ CH—NHOC₂H₅ H CH₃ 1.308 CH₃ CH₃ H 2 CH₂ CH—NHOC₂H₅ H CH₃ 1.309 CH₃ CH₃ H 0 CH₂ CH—N(CH₃)OC₂H₅ H CH₃ 1.310 CH₃ CH₃ H 2 CH₂ CH—N(CH₃)OC₂H₅ H CH₃ 1.311 CH₃ CH₃ H 0 CH₂ C═N—NH₂ H CH₃ 1.312 CH₃ CH₃ H 2 CH₂ C═N—NH₂ H CH₃ 1.313 CH₃ CH₃ H 0 CH₂ C═N—N(CH₃)₂ H CH₃ 1.314 CH₃ CH₃ H 2 CH₂ C═N—N(CH₃)₂ H CH₃ 1.315 CH₃ CH₃ H 0 CH₂ C(CH₃)—OCH₃ H CH₃ 1.316 CH₃ CH₃ H 2 CH₂ C(CH₃)—OCH₃ H CH₃ 1.317 CH₃ CH₃ H 0 CH₂ O H CH₃ 1.318 CH₃ CH₃ H 2 CH₂ O H CH₃ 1.319 C₂H₅ H H 0 CH₂ CH—NHCH₃ H CH₃ 1.320 C₂H₅ H H 2 CH₂ CH—NHCH₃ H CH₃ 1.321 C₂H₅ H H 0 CH₂ CH—NHC₂H₅ H CH₃ 1.322 C₂H₅ H H 2 CH₂ CH—NHC₂H₅ H CH₃ 1.323 C₂H₅ H H 0 CH₂ CH—N(CH₃)₂ H CH₃ 1.324 C₂H₅ H H 2 CH₂ CH—N(CH₃)₂ H CH₃ 1.325 C₂H₅ H H 0 CH₂ CH—NHOC₂H₅ H CH₃ 1.326 C₂H₅ H H 2 CH₂ CH—NHOC₂H₅ H CH₃ 1.327 C₂H₅ H H 0 CH₂ CH—N(CH₃)OC₂H₅ H CH₃ 1.328 C₂H₅ H H 2 CH₂ CH—N(CH₃)OC₂H₅ H CH₃ 1.329 C₂H₅ H H 0 CH₂ C═N—NH₂ H CH₃ 1.330 C₂H₅ H H 2 CH₂ C═N—NH₂ H CH₃ 1.331 C₂H₅ H H 0 CH₂ C═N—N(CH₃)₂ H CH₃ 1.332 C₂H₅ H H 2 CH₂ C═N—N(CH₃)₂ H CH₃ 1.333 C₂H₅ H H 0 CH₂ C(CH₃)—OCH₃ H CH₃ 1.334 C₂H₅ H H 2 CH₂ C(CH₃)—OCH₃ H CH₃ 1.335 C₂H₅ H H 0 CH₂ O H CH₃ 1.336 C₂H₅ H H 2 CH₂ O H CH₃ 1.337 CH₃ CH₃ H 0 CH₂ CH—NHCH₃ H Cl 1.338 CH₃ CH₃ H 2 CH₂ CH—NHCH₃ H Cl 1.339 CH₃ CH₃ H 0 CH₂ CH—NHC₂H₅ H Cl 1.340 CH₃ CH₃ H 2 CH₂ CH—NHC₂H₅ H Cl 1.341 CH₃ CH₃ H 0 CH₂ CH—N(CH₃)₂ H Cl 1.342 CH₃ CH₃ H 2 CH₂ CH—N(CH₃)₂ H Cl 1.343 CH₃ CH₃ H 0 CH₂ CH—NHOC₂H₅ H Cl 1.344 CH₃ CH₃ H 2 CH₂ CH—NHOC₂H₅ H Cl 1.345 CH₃ CH₃ H 0 CH₂ CH—N(CH₃)OC₂H₅ H Cl 1.346 CH₃ CH₃ H 2 CH₂ CH—N(CH₃)OC₂H₅ H Cl 1.347 CH₃ CH₃ H 0 CH₂ C═N—NH₂ H Cl 1.348 CH₃ CH₃ H 2 CH₂ C═N—NH₂ H Cl 1.349 CH₃ CH₃ H 0 CH₂ C═N—N(CH₃)₂ H Cl 1.350 CH₃ CH₃ H 2 CH₂ C═N—N(CH₃)₂ H Cl 1.351 CH₃ CH₃ H 0 CH₂ C(CH₃)—OCH₃ H Cl 1.352 CH₃ CH₃ H 2 CH₂ C(CH₃)—OCH₃ H Cl 1.353 CH₃ CH₃ H 0 CH₂ O H Cl 1.354 CH₃ CH₃ H 2 CH₂ O H Cl 1.355 C₂H₅ H H 0 CH₂ CH—NHCH₃ H Cl 1.356 C₂H₅ H H 2 CH₂ CH—NHCH₃ H Cl 1.357 C₂H₅ H H 0 CH₂ CH—NHC₂H₅ H Cl 1.358 C₂H₅ H H 2 CH₂ CH—NHC₂H₅ H Cl 1.359 C₂H₅ H H 0 CH₂ CH—N(CH₃)₂ H Cl 1.360 C₂H₅ H H 2 CH₂ CH—N(CH₃)₂ H Cl 1.361 C₂H₅ H H 0 CH₂ CH—NHOC₂H₅ H Cl 1.362 C₂H₅ H H 2 CH₂ CH—NHOC₂H₅ H Cl 1.363 C₂H₅ H H 0 CH₂ CH—N(CH₃)OC₂H₅ H Cl 1.364 C₂H₅ H H 2 CH₂ CH—N(CH₃)OC₂H₅ H Cl 1.365 C₂H₅ H H 0 CH₂ C═N—NH₂ H Cl 1.366 C₂H₅ H H 2 CH₂ C═N—NH₂ H Cl 1.367 C₂H₅ H H 0 CH₂ C═N—N(CH₃)₂ H Cl 1.368 C₂H₅ H H 2 CH₂ C═N—N(CH₃)₂ H Cl 1.369 C₂H₅ H H 0 CH₂ C(CH₃)—OCH₃ H Cl 1.370 C₂H₅ H H 2 CH₂ C(CH₃)—OCH₃ H Cl 1.371 C₂H₅ H H 0 CH₂ O H Cl 1.372 C₂H₅ H H 2 CH₂ O H Cl 1.373 CH₃ CH₃ H 0 (CH₂)₂ CH—NHCH₃ H H 1.374 CH₃ CH₃ H 2 (CH₂)₂ CH—NHCH₃ H H 1.375 CH₃ CH₃ H 0 (CH₂)₂ CH—NHC₂H₅ H H 1.376 CH₃ CH₃ H 2 (CH₂)₂ CH—NHC₂H₅ H H 1.377 CH₃ CH₃ H 0 (CH₂)₂ CH—N(CH₃)₂ H H 1.378 CH₃ CH₃ H 2 (CH₂)₂ CH—N(CH₃)₂ H H 1.379 CH₃ CH₃ H 0 (CH₂)₂ CH—NHOC₂H₅ H H 1.380 CH₃ CH₃ H 2 (CH₂)₂ CH—NHOC₂H₅ H H 1.381 CH₃ CH₃ H 0 (CH₂)₂ CH—N(CH₃)OC₂H₅ H H 1.382 CH₃ CH₃ H 2 (CH₂)₂ CH—N(CH₃)OC₂H₅ H H 1.383 CH₃ CH₃ H 0 (CH₂)₂ C═N—NH₂ H H 1.384 CH₃ CH₃ H 2 (CH₂)₂ C═N—NH₂ H H 1.385 CH₃ CH₃ H 0 (CH₂)₂ C═N—N(CH₃)₂ H H 1.386 CH₃ CH₃ H 2 (CH₂)₂ C═N—N(CH₃)₂ H H 1.387 CH₃ CH₃ H 0 (CH₂)₂ C(CH₃)—OCH₃ H H 1.388 CH₃ CH₃ H 2 (CH₂)₂ C(CH₃)—OCH₃ H H 1.389 CH₃ CH₃ H 0 (CH₂)₂ O H H 1.390 CH₃ CH₃ H 2 (CH₂)₂ O H H 1.391 C₂H₅ H H 0 (CH₂)₂ CH—NHCH₃ H H 1.392 C₂H₅ H H 2 (CH₂)₂ CH—NHCH₃ H H 1.393 C₂H₅ H H 0 (CH₂)₂ CH—NHC₂H₅ H H 1.394 C₂H₅ H H 2 (CH₂)₂ CH—NHC₂H₅ H H 1.395 C₂H₅ H H 0 (CH₂)₂ CH—N(CH₃)₂ H H 1.396 C₂H₅ H H 2 (CH₂)₂ CH—N(CH₃)₂ H H 1.397 C₂H₅ H H 0 (CH₂)₂ CH—NHOC₂H₅ H H 1.398 C₂H₅ H H 2 (CH₂)₂ CH—NHOC₂H₅ H H 1.399 C₂H₅ H H 0 (CH₂)₂ CH—N(CH₃)OC₂H₅ H H 1.400 C₂H₅ H H 2 (CH₂)₂ CH—N(CH₃)OC₂H₅ H H 1.401 C₂H₅ H H 0 (CH₂)₂ C═N—NH₂ H H 1.402 C₂H₅ H H 2 (CH₂)₂ C═N—NH₂ H H 1.403 C₂H₅ H H 0 (CH₂)₂ C═N—N(CH₃)₂ H H 1.404 C₂H₅ H H 2 (CH₂)₂ C═N—N(CH₃)₂ H H 1.405 C₂H₅ H H 0 (CH₂)₂ C(CH₃)—OCH₃ H H 1.406 C₂H₅ H H 2 (CH₂)₂ C(CH₃)—OCH₃ H H 1.407 C₂H₅ H H 0 (CH₂)₂ O H H 1.408 C₂H₅ H H 2 (CH₂)₂ O H H 1.409 CH₃ CH₃ H 0 (CH₂)₂ CH—NHCH₃ H CH₃ 1.410 CH₃ CH₃ H 2 (CH₂)₂ CH—NHCH₃ H CH₃ 1.411 CH₃ CH₃ H 0 (CH₂)₂ CH—NHC₂H₅ H CH₃ 1.412 CH₃ CH₃ H 2 (CH₂)₂ CH—NHC₂H₅ H CH₃ 1.413 CH₃ CH₃ H 0 (CH₂)₂ CH—N(CH₃)₂ H CH₃ 1.414 CH₃ CH₃ H 2 (CH₂)₂ CH—N(CH₃)₂ H CH₃ 1.415 CH₃ CH₃ H 0 (CH₂)₂ CH—NHOC₂H₅ H CH₃ 1.416 CH₃ CH₃ H 2 (CH₂)₂ CH—NHOC₂H₅ H CH₃ 1.417 CH₃ CH₃ H 0 (CH₂)₂ CH—N(CH₃)OC₂H₅ H CH₃ 1.418 CH₃ CH₃ H 2 (CH₂)₂ CH—N(CH₃)OC₂H₅ H CH₃ 1.419 CH₃ CH₃ H 0 (CH₂)₂ C═N—NH₂ H CH₃ 1.420 CH₃ CH₃ H 2 (CH₂)₂ C═N—NH₂ H CH₃ 1.421 CH₃ CH₃ H 0 (CH₂)₂ C═N—N(CH₃)₂ H CH₃ 1.422 CH₃ CH₃ H 2 (CH₂)₂ C═N—N(CH₃)₂ H CH₃ 1.423 CH₃ CH₃ H 0 (CH₂)₂ C(CH₃)—OCH₃ H CH₃ 1.424 CH₃ CH₃ H 2 (CH₂)₂ C(CH₃)—OCH₃ H CH₃ 1.425 CH₃ CH₃ H 0 (CH₂)₂ O H CH₃ 1.426 CH₃ CH₃ H 2 (CH₂)₂ O H CH₃ 1.427 C₂H₅ H H 0 (CH₂)₂ CH—NHCH₃ H CH₃ 1.428 C₂H₅ H H 2 (CH₂)₂ CH—NHCH₃ H CH₃ 1.429 C₂H₅ H H 0 (CH₂)₂ CH—NHC₂H₅ H CH3. 1.430 C₂H₅ H H 2 (CH₂)₂ CH—NHC₂H₅ H CH₃ 1.431 C₂H₅ H H 0 (CH₂)₂ CH—N(CH₃)₂ H CH₃ 1.432 C₂H₅ H H 2 (CH₂)₂ CH—N(CH₃)₂ H CH₃ 1.433 C₂H₅ H H 0 (CH₂)₂ CH—NHOC₂H₅ H CH₃ 1.434 C₂H₅ H H 2 (CH₂)₂ CH—NHOC₂H₅ H CH₃ 1.435 C₂H₅ H H 0 (CH₂)₂ CH—N(CH₃)OC₂H₅ H CH₃ 1.436 C₂H₅ H H 2 (CH₂)₂ CH—N(CH₃)OC₂H₅ H CH₃ 1.437 C₂H₅ H H 0 (CH₂)₂ C═N—NH₂ H CH₃ 1.438 C₂H₅ H H 2 (CH₂)₂ C═N—NH₂ H CH₃ 1.439 C₂H₅ H H 0 (CH₂)₂ C═N—N(CH₃)₂ H CH₃ 1.440 C₂H₅ H H 2 (CH₂)₂ C═N—N(CH₃)₂ H CH₃ 1.441 C₂H₅ H H 0 (CH₂)₂ C(CH₃)—OCH₃ H CH₃ 1.442 C₂H₅ H H 2 (CH₂)₂ C(CH₃)—OCH₃ H CH₃ 1.443 C₂H₅ H H 0 (CH₂)₂ O H CH₃ 1.444 C₂H₅ H H 2 (CH₂)₂ O H CH₃ 1.445 CH₃ CH₃ H 0 (CH₂)₂ CH—NHCH₃ H Cl 1.446 CH₃ CH₃ H 2 (CH₂)₂ CH—NHCH₃ H Cl 1.447 CH₃ CH₃ H 0 (CH₂)₂ CH—NHC₂H₅ H Cl 1.448 CH₃ CH₃ H 2 (CH₂)₂ CH—NHC₂H₅ H Cl 1.449 CH₃ CH₃ H 0 (CH₂)₂ CH—N(CH₃)₂ H Cl 1.450 CH₃ CH₃ H 2 (CH₂)₂ CH—N(CH₃)₂ H Cl 1.451 CH₃ CH₃ H 0 (CH₂)₂ CH—NHOC₂H₅ H Cl 1.452 CH₃ CH₃ H 2 (CH₂)₂ CH—NHOC₂H₅ H Cl 1.453 CH₃ CH₃ H 0 (CH₂)₂ CH—N(CH₃)OC₂H₅ H Cl 1.454 CH₃ CH₃ H 2 (CH₂)₂ CH—N(CH₃)OC₂H₅ H Cl 1.455 CH₃ CH₃ H 0 (CH₂)₂ C═N—NH₂ H Cl 1.456 CH₃ CH₃ H 2 (CH₂)₂ C═N—NH₂ H Cl 1.457 CH₃ CH₃ H 0 (CH₂)₂ C═N—N(CH₃)₂ H Cl 1.458 CH₃ CH₃ H 2 (CH₂)₂ C═N—N(CH₃)₂ H Cl 1.459 CH₃ CH₃ H 0 (CH₂)₂ C(CH₃)—OCH₃ H Cl 1.460 CH₃ CH₃ H 2 (CH₂)₂ C(CH₃)—OCH₃ H Cl 1.461 CH₃ CH₃ H 0 (CH₂)₂ O H Cl 1.462 CH₃ CH₃ H 2 (CH₂)₂ O H Cl 1.463 C₂H₅ H H 0 (CH₂)₂ CH—NHCH₃ H Cl 1.464 C₂H₅ H H 2 (CH₂)₂ CH—NHCH₃ H Cl 1.465 C₂H₅ H H 0 (CH₂)₂ CH—NHC₂H₅ H Cl 1.466 C₂H₅ H H 2 (CH₂)₂ CH—NHC₂H₅ H Cl 1.467 C₂H₅ H H 0 (CH₂)₂ CH—N(CH₃)₂ H Cl 1.468 C₂H₅ H H 2 (CH₂)₂ CH—N(CH₃)₂ H Cl 1.469 C₂H₅ H H 0 (CH₂)₂ CH—NHOC₂H₅ H Cl 1.470 C₂H₅ H H 2 (CH₂)₂ CH—NHOC₂H₅ H Cl 1.471 C₂H₅ H H 0 (CH₂)₂ CH—N(CH₃)OC₂H₅ H Cl 1.472 C₂H₅ H H 2 (CH₂)₂ CH—N(CH₃)OC₂H₅ H Cl 1.473 C₂H₅ H H 0 (CH₂)₂ C═N—NH₂ H Cl 1.474 C₂H₅ H H 2 (CH₂)₂ C═N—NH₂ H Cl 1.475 C₂H₅ H H 0 (CH₂)₂ C═N—N(CH₃)₂ H Cl 1.476 C₂H₅ H H 2 (CH₂)₂ C═N—N(CH₃)₂ H Cl 1.477 C₂H₅ H H 0 (CH₂)₂ C(CH₃)—OCH₃ H Cl 1.478 C₂H₅ H H 2 (CH₂)₂ C(CH₃)—OCH₃ H Cl 1.479 C₂H₅ H H 0 (CH₂)₂ O H Cl 1.480 C₂H₅ H H 2 (CH₂)₂ O H Cl 1.481 CH₃ CH₃ H 0 (CH₂)₂ CH—NHCH₃ CH₃ CH₃ 1.482 CH₃ CH₃ H 2 (CH₂)₂ CH—NHCH₃ CH₃ CH₃ 1.483 CH₃ CH₃ H 0 (CH₂)₂ CH—NHC₂H₅ CH₃ CH₃ 1.484 CH₃ CH₃ H 2 (CH₂)₂ CH—NHC₂H₅ CH₃ CH₃ 1.485 CH₃ CH₃ H 0 (CH₂)₂ CH—N(CH₃)₂ CH₃ CH₃ 1.486 CH₃ CH₃ H 2 (CH₂)₂ CH—N(CH₃)₂ CH₃ CH₃ 1.487 CH₃ CH₃ H 0 (CH₂)₂ CH—NHOC₂H₅ CH₃ CH₃ 1.488 CH₃ CH₃ H 2 (CH₂)₂ CH—NHOC₂H₅ CH₃ CH₃ 1.489 CH₃ CH₃ H 0 (CH₂)₂ CH—N(CH₃)OC₂H₅ CH₃ CH₃ 1.490 CH₃ CH₃ H 2 (CH₂)₂ CH—N(CH₃)OC₂H₅ CH₃ CH₃ 1.491 CH₃ CH₃ H 0 (CH₂)₂ C═N—NH₂ CH₃ CH₃ 1.492 CH₃ CH₃ H 2 (CH₂)₂ C═N—NH₂ CH₃ CH₃ 1.493 CH₃ CH₃ H 0 (CH₂)₂ C═N—N(CH₃)₂ CH₃ CH₃ 1.494 CH₃ CH₃ H 2 (CH₂)₂ C═N—N(CH₃)₂ CH₃ CH₃ 1.495 CH₃ CH₃ H 0 (CH₂)₂ C(CH₃)—OCH₃ CH₃ CH₃ 1.496 CH₃ CH₃ H 2 (CH₂)₂ C(CH₃)—OCH₃ CH₃ CH₃ 1.497 CH₃ CH₃ H 0 (CH₂)₂ O CH₃ CH₃ 1.498 CH₃ CH₃ H 2 (CH₂)₂ O CH₃ CH₃ 1.499 C₂H₅ H H 0 (CH₂)₂ CH—NHCH₃ CH₃ CH₃ 1.500 C₂H₅ H H 2 (CH₂)₂ CH—NHCH₃ CH₃ CH₃ 1.501 C₂H₅ H H 0 (CH₂)₂ CH—NHC₂H₅ CH₃ CH₃ 1.502 C₂H₅ H H 2 (CH₂)₂ CH—NHC₂H₅ CH₃ CH₃ 1.503 C₂H₅ H H 0 (CH₂)₂ CH—N(CH₃)₂ CH₃ CH₃ 1.504 C₂H₅ H H 2 (CH₂)₂ CH—N(CH₃)₂ CH₃ CH₃ 1.505 C₂H₅ H H 0 (CH₂)₂ CH—NHOC₂H₅ CH₃ CH₃ 1.506 C₂H₅ H H 2 (CH₂)₂ CH—NHOC₂H₅ CH₃ CH₃ 1.507 C₂H₅ H H 0 (CH₂)₂ CH—N(CH₃)OC₂H₅ CH₃ CH₃ 1.508 C₂H₅ H H 2 (CH₂)₂ CH—N(CH₃)OC₂H₅ CH₃ CH₃ 1.509 C₂H₅ H H 0 (CH₂)₂ C═N—NH₂ CH₃ CH₃ 1.510 C₂H₅ H H 2 (CH₂)₂ C═N—NH₂ CH₃ CH₃ 1.511 C₂H₅ H H 0 (CH₂)₂ C═N—N(CH₃)₂ CH₃ CH₃ 1.512 C₂H₅ H H 2 (CH₂)₂ C═N—N(CH₃)₂ CH₃ CH₃ 1.513 C₂H₅ H H 0 (CH₂)₂ C(CH₃)—OCH₃ CH₃ CH₃ 1.514 C₂H₅ H H 2 (CH₂)₂ C(CH₃)—OCH₃ CH₃ CH₃ 1.515 C₂H₅ H H 0 (CH₂)₂ O CH₃ CH₃ 1.516 C₂H₅ H H 2 (CH₂)₂ O CH₃ CH₃ 1.517 CH₃ CH₃ H 0 (CH₂)₂ CH—NHCH₃ Cl Cl 1.518 CH₃ CH₃ H 2 (CH₂)₂ CH—NHCH₃ Cl Cl 1.519 CH₃ CH₃ H 0 (CH₂)₂ CH—NHC₂H₅ Cl Cl 1.520 CH₃ CH₃ H 2 (CH₂)₂ CH—NHC₂H₅ Cl Cl 1.521 CH₃ CH₃ H 0 (CH₂)₂ CH—N(CH₃)₂ Cl Cl 1.522 CH₃ CH₃ H 2 (CH₂)₂ CH—N(CH₃)₂ Cl Cl 1.523 CH₃ CH₃ H 0 (CH₂)₂ CH—NHOC₂H₅ Cl Cl 1.524 CH₃ CH₃ H 2 (CH₂)₂ CH—NHOC₂H₅ Cl Cl 1.525 CH₃ CH₃ H 0 (CH₂)₂ CH—N(CH₃)OC₂H₅ Cl Cl 1.526 CH₃ CH₃ H 2 (CH₂)₂ CH—N(CH₃)OC₂H₅ Cl Cl 1.527 CH₃ CH₃ H 0 (CH₂)₂ C═N—NH₂ Cl Cl 1.528 CH₃ CH₃ H 2 (CH₂)₂ C═N—NH₂ Cl Cl 1.529 CH₃ CH₃ H 0 (CH₂)₂ C═N—N(CH₃)₂ Cl Cl 1.530 CH₃ CH₃ H 2 (CH₂)₂ C═N—N(CH₃)₂ Cl Cl 1.531 CH₃ CH₃ H 0 (CH₂)₂ C(CH₃)—OCH₃ Cl Cl 1.532 CH₃ CH₃ H 2 (CH₂)₂ C(CH₃)—OCH₃ Cl Cl 1.533 CH₃ CH₃ H 0 (CH₂)₂ O Cl Cl 1.534 CH₃ CH₃ H 2 (CH₂)₂ O Cl Cl 1.535 C₂H₅ H H 0 (CH₂)₂ CH—NHCH₃ Cl Cl 1.536 C₂H₅ H H 2 (CH₂)₂ CH—NHCH₃ Cl Cl 1.537 C₂H₅ H H 0 (CH₂)₂ CH—NHC₂H₅ Cl Cl 1.538 C₂H₅ H H 2 (CH₂)₂ CH—NHC₂H₅ Cl Cl 1.539 C₂H₅ H H 0 (CH₂)₂ CH—N(CH₃)₂ Cl Cl 1.540 C₂H₅ H H 2 (CH₂)₂ CH—N(CH₃)₂ Cl Cl 1.541 C₂H₅ H H 0 (CH₂)₂ CH—NHOC₂H₅ Cl Cl 1.542 C₂H₅ H H 2 (CH₂)₂ CH—NHOC₂H₅ Cl Cl 1.543 C₂H₅ H H 0 (CH₂)₂ CH—N(CH₃)OC₂H₅ Cl Cl 1.544 C₂H₅ H H 2 (CH₂)₂ CH—N(CH₃)OC₂H₅ Cl Cl 1.545 C₂H₅ H H 0 (CH₂)₂ C═N—NH₂ Cl Cl 1.546 C₂H₅ H H 2 (CH₂)₂ C═N—NH₂ Cl Cl 1.547 C₂H₅ H H 0 (CH₂)₂ C═N—N(CH₃)₂ Cl Cl 1.548 C₂H₅ H H 2 (CH₂)₂ C═N—N(CH₃)₂ Cl Cl 1.549 C₂H₅ H H 0 (CH₂)₂ C(CH₃)—OCH₃ Cl Cl 1.550 C₂H₅ H H 2 (CH₂)₂ C(CH₃)—OCH₃ Cl Cl 1.551 C₂H₅ H H 0 (CH₂)₂ O Cl Cl 1.552 C₂H₅ H H 2 (CH₂)₂ O Cl Cl 1.553 CH₃ CH₃ H 0 (CH₂)₂ C═O Cl Cl 1.554 CH₃ CH₃ H 2 (CH₂)₂ C═O Cl Cl 1.555 CH₃ CH₃ H 0 (CH₂)₂ CHOCH₃ Cl Cl 1.556 CH₃ CH₃ H 2 (CH₂)₂ CHOCH₃ Cl Cl 1.557 CH₃ CH₃ H 0 (CH₂)₂ CHOC₂H₅ Cl Cl 1.558 CH₃ CH₃ H 2 (CH₂)₂ CHOC₂H₅ Cl Cl 1.559 CH₃ CH₃ H 0 (CH₂)₂ CHOiPr Cl Cl 1.560 CH₃ CH₃ H 2 (CH₂)₂ CHOiPr Cl Cl 1.561 CH₃ CH₃ H 0 (CH₂)₂ CHOH Cl Cl 1.562 CH₃ CH₃ H 2 (CH₂)₂ CHOH Cl Cl 1.563 CH₃ CH₃ H 0 (CH₂)₂ C═NOCH₃ Cl Cl 1.564 CH₃ CH₃ H 2 (CH₂)₂ C═NOCH₃ Cl Cl 1.565 CH₃ CH₃ H 0 (CH₂)₂ C═NOC₂H₅ Cl Cl 1.566 CH₃ CH₃ H 2 (CH₂)₂ C═NOC₂H₅ Cl Cl 1.567 CH₃ CH₃ H 0 (CH₂)₂ C═NOiPr Cl Cl 1.568 CH₃ CH₃ H 2 (CH₂)₂ C═NOiPr Cl Cl 1.569 CH₃ CH₃ H 0 (CH₂)₂ C═NOCH₂CH═CHCl Cl Cl 1.570 CH₃ CH₃ H 2 (CH₂)₂ C═NOCH₂CH═CHCl Cl Cl 1.571 CH₃ CH₃ H 0 (CH₂)₂ C═NOCH₂C₆H₅ Cl Cl 1.572 CH₃ CH₃ H 2 (CH₂)₂ C═NOCH₂C₆H₅ Cl Cl 1.573 CH₃ CH₃ H 0 (CH₂)₂ C(CH₃)₂ Cl Cl 1.574 CH₃ CH₃ H 2 (CH₂)₂ C(CH₃)₂ Cl Cl 1.575 C₂H₅ H H 0 (CH₂)₂ C═O Cl Cl 1.576 C₂H₅ H H 2 (CH₂)₂ C═O Cl Cl 1.577 C₂H₅ H H 0 (CH₂)₂ CHOCH₃ Cl Cl 1.578 C₂H₅ H H 2 (CH₂)₂ CHOCH₃ Cl Cl 1.579 C₂H₅ H H 0 (CH₂)₂ CHOC₂H₅ Cl Cl 1.580 C₂H₅ H H 2 (CH₂)₂ CHOC₂H₅ Cl Cl 1.581 C₂H₅ H H 0 (CH₂)₂ CHOiPr Cl Cl 1.582 C₂H₅ H H 2 (CH₂)₂ CHOiPr Cl Cl 1.583 C₂H₅ H H 0 (CH₂)₂ CHOH Cl Cl 1.584 C₂H₅ H H 2 (CH₂)₂ CHOH Cl Cl 1.585 C₂H₅ H H 0 (CH₂)₂ C═NOCH₃ Cl Cl 1.586 C₂H₅ H H 2 (CH₂)₂ C═NOCH₃ Cl Cl 1.587 C₂H₅ H H 0 (CH₂)₂ C═NOC₂H₅ Cl Cl 1.588 C₂H₅ H H 2 (CH₂)₂ C═NOC₂H₅ Cl Cl 1.589 C₂H₅ H H 0 (CH₂)₂ C═NOiPr Cl Cl 1.590 C₂H₅ H H 2 (CH₂)₂ C═NOiPr Cl Cl 1.591 C₂H₅ H H 0 (CH₂)₂ C═NOCH₂CH═CHCl Cl Cl 1.592 C₂H₅ H H 2 (CH₂)₂ C═NOCH₂CH═CHCl Cl Cl 1.593 C₂H₅ H H 0 (CH₂)₂ C═NOCH₂C₆H₅ Cl Cl 1.594 C₂H₅ H H 2 (CH₂)₂ C═NOCH₂C₆H₅ Cl Cl 1.595 C₂H₅ H H 0 (CH₂)₂ C(CH₃)₂ Cl Cl 1.596 C₂H₅ H H 2 (CH₂)₂ C(CH₃)₂ Cl Cl 1.597 CH₃ CH₃ H 0 (CH₂)₂ C═O CH₃ CH₃ 1.598 CH₃ CH₃ H 2 (CH₂)₂ C═O CH₃ CH₃ 1.599 CH₃ CH₃ H 0 (CH₂)₂ CHOCH₃ CH₃ CH₃ 1.600 CH₃ CH₃ H 2 (CH₂)₂ CHOCH₃ CH₃ CH₃ 1.601 CH₃ CH₃ H 0 (CH₂)₂ CHOC₂H₅ CH₃ CH₃ 1.602 CH₃ CH₃ H 2 (CH₂)₂ CHOC₂H₅ CH₃ CH₃ 1.603 CH₃ CH₃ H 0 (CH₂)₂ CHOiPr CH₃ CH₃ 1.604 CH₃ CH₃ H 2 (CH₂)₂ CHOiPr CH₃ CH₃ 1.605 CH₃ CH₃ H 0 (CH₂)₂ CHOH CH₃ CH₃ 1.606 CH₃ CH₃ H 2 (CH₂)₂ CHOH CH₃ CH₃ 1.607 CH₃ CH₃ H 0 (CH₂)₂ C═NOCH₃ CH₃ CH₃ 1.608 CH₃ CH₃ H 2 (CH₂)₂ C═NOCH₃ CH₃ CH₃ 1.609 CH₃ CH₃ H 0 (CH₂)₂ C═NOC₂H₅ CH₃ CH₃ 1.610 CH₃ CH₃ H 2 (CH₂)₂ C═NOC₂H₅ CH₃ CH₃ 1.611 CH₃ CH₃ H 0 (CH₂)₂ C═NOiPr CH₃ CH₃ 1.612 CH₃ CH₃ H 2 (CH₂)₂ C═NOiPr CH₃ CH₃ 1.613 CH₃ CH₃ H 0 (CH₂)₂ C═NOCH₂CH═CHCl CH₃ CH₃ 1.614 CH₃ CH₃ H 2 (CH₂)₂ C═NOCH₂CH═CHCl CH₃ CH₃ 1.615 CH₃ CH₃ H 0 (CH₂)₂ C═NOCH₂C₆H₅ CH₃ CH₃ 1.616 CH₃ CH₃ H 2 (CH₂)₂ C═NOCH₂C₆H₅ CH₃ CH₃ 1.617 CH₃ CH₃ H 0 (CH₂)₂ C(CH₃)₂ CH₃ CH₃ 1.618 CH₃ CH₃ H 2 (CH₂)₂ C(CH₃)₂ CH₃ CH₃ 1.619 C₂H₅ H H 0 (CH₂)₂ C═O CH₃ CH₃ 1.620 C₂H₅ H H 2 (CH₂)₂ C═O CH₃ CH₃ 1.621 C₂H₅ H H 0 (CH₂)₂ CHOCH₃ CH₃ CH₃ 1.622 C₂H₅ H H 2 (CH₂)₂ CHOCH₃ CH₃ CH₃ 1.623 C₂H₅ H H 0 (CH₂)₂ CHOC₂H₅ CH₃ CH₃ 1.624 C₂H₅ H H 2 (CH₂)₂ CHOC₂H₅ CH₃ CH₃ 1.625 C₂H₅ H H 0 (CH₂)₂ CHOiPr CH₃ CH₃ 1.626 C₂H₅ H H 2 (CH₂)₂ CHOiPr CH₃ CH₃ 1.627 C₂H₅ H H 0 (CH₂)₂ CHOH CH₃ CH₃ 1.628 C₂H₅ H H 2 (CH₂)₂ CHOH CH₃ CH₃ 1.629 C₂H₅ H H 0 (CH₂)₂ C═NOCH₃ CH₃ CH₃ 1.630 C₂H₅ H H 2 (CH₂)₂ C═NOCH₃ CH₃ CH₃ 1.631 C₂H₅ H H 0 (CH₂)₂ C═NOC₂H₅ CH₃ CH₃ 1.632 C₂H₅ H H 2 (CH₂)₂ C═NOC₂H₅ CH₃ CH₃ 1.633 C₂H₅ H H 0 (CH₂)₂ C═NOiPr CH₃ CH₃ 1.634 C₂H₅ H H 2 (CH₂)₂ C═NOiPr CH₃ CH₃ 1.635 C₂H₅ H H 0 (CH₂)₂ C═NOCH₂CH═CHCl CH₃ CH₃ 1.636 C₂H₅ H H 2 (CH₂)₂ C═NOCH₂CH═CHCl CH₃ CH₃ 1.637 C₂H₅ H H 0 (CH₂)₂ C═NOCH₂C₆H₅ CH₃ CH₃ 1.638 C₂H₅ H H 2 (CH₂)₂ C═NOCH₂C₆H₅ CH₃ CH₃ 1.639 C₂H₅ H H 0 (CH₂)₂ C(CH₃)₂ CH₃ CH₃ 1.640 C₂H₅ H H 2 (CH₂)₂ C(CH₃)₂ CH₃ CH₃

TABLE 2 Compounds of the formula

No. R¹⁵ R¹⁶ R¹⁷ n X Y L M 2.1 CH₃ CH₃ H 0 N COCH₃ H CH₃ 2.2 CH₃ CH₃ H 2 N COCH₃ H CH₃ 2.3 CH₃ CH₃ H 0 N COC₂H₅ H CH₃ 2.4 CH₃ CH₃ H 2 N COC₂H₅ H CH₃ 2.5 CH₃ CH₃ H 0 N COiPr H CH₃ 2.6 CH₃ CH₃ H 2 N COiPr H CH₃ 2.7 C₂H₅ H H 0 N COCH₃ H CH₃ 2.8 C₂H₅ H H 2 N COCH₃ H CH₃ 2.9 C₂H₅ H H 0 N COC₂H₅ H CH₃ 2.10 C₂H₅ H H 2 N COC₂H₅ H CH₃ 2.11 C₂H₅ H H 0 N COiPr H CH₃ 2.12 C₂H₅ H H 2 N COiPr H CH₃ 2.13 CH₃ CH₃ H 0 CH COCH₃ H CH₃ 2.14 CH₃ CH₃ H 2 CH COCH₃ H CH₃ 2.15 CH₃ CH₃ H 0 CH COC₂H₅ H CH₃ 2.16 CH₃ CH₃ H 2 CH COC₂H₅ H CH₃ 2.17 CH₃ CH₃ H 0 CH COiPr H CH₃ 2.18 CH₃ CH₃ H 2 CH COiPr H CH₃ 2.19 C₂H₅ H H 0 CH COCH₃ H CH₃ 2.20 C₂H₅ H H 2 CH COCH₃ H CH₃ 2.21 C₂H₅ H H 0 CH COC₂H₅ H CH₃ 2.22 C₂H₅ H H 2 CH COC₂H₅ H CH₃ 2.23 C₂H₅ H H 0 CH COiPr H CH₃ 2.24 C₂H₅ H H 2 CH COiPr H CH₃ 2.25 CH₃ CH₃ H 0 N COCH₃ H Cl 2.26 CH₃ CH₃ H 2 N COCH₃ H Cl 2.27 CH₃ CH₃ H 0 N COC₂H₅ H Cl 2.28 CH₃ CH₃ H 2 N COC₂H₅ H Cl 2.29 CH₃ CH₃ H 0 N COiPr H Cl 2.30 CH₃ CH₃ H 2 N COiPr H Cl 2.31 C₂H₅ H H 0 N COCH₃ H Cl 2.32 C₂H₅ H H 2 N COCH₃ H Cl 2.33 C₂H₅ H H 0 N COC₂H₅ H Cl 2.34 C₂H₅ H H 2 N COC₂H₅ H Cl 2.35 C₂H₅ H H 0 N COiPr H Cl 2.36 C₂H₅ H H 2 N COiPr H Cl 2.37 CH₃ CH₃ H 0 CH COCH₃ H Cl 2.38 CH₃ CH₃ H 2 CH COCH₃ H Cl 2.39 CH₃ CH₃ H 0 CH COC₂H₅ H Cl 2.40 CH₃ CH₃ H 2 CH COC₂H₅ H Cl 2.41 CH₃ CH₃ H 0 CH COiPr H Cl 2.42 CH₃ CH₃ H 2 CH COiPr H Cl 2.43 C₂H₅ H H 0 CH COCH₃ H Cl 2.44 C₂H₅ H H 2 CH COCH₃ H Cl 2.45 C₂H₅ H H 0 CH COC₂H₅ H Cl 2.46 C₂H₅ H H 2 CH COC₂H₅ H Cl 2.47 C₂H₅ H H 0 CH COiPr H Cl 2.48 C₂H₅ H H 2 CH COiPr H Cl

TABLE 3 Compounds of the formula

No. R¹⁵ R¹⁶ R¹⁷ n Y L M 3.1 CH₃ CH₃ H 0 COCH₃ H CH₃ 3.2 CH₃ CH₃ H 2 COCH₃ H CH₃ 3.3 CH₃ CH₃ H 0 COC₂H₅ H CH₃ 3.4 CH₃ CH₃ H 2 COC₂H₅ H CH₃ 3.5 CH₃ CH₃ H 0 COiPr H CH₃ 3.6 CH₃ CH₃ H 2 COiPr H CH₃ 3.7 C₂H₅ H H 0 COCH₃ H CH₃ 3.8 C₂H₅ H H 2 COCH₃ H CH₃ 3.9 C₂H₅ H H 0 COC₂H₅ H CH₃ 3.10 C₂H₅ H H 2 COC₂H₅ H CH₃ 3.11 C₂H₅ H H 0 COiPr H CH₃ 3.12 C₂H₅ H H 2 COiPr H CH₃ 3.13 CH₃ CH₃ H 0 COCH₃ H Cl 3.14 CH₃ CH₃ H 2 COCH₃ H Cl 3.15 CH₃ CH₃ H 0 COC₂H₅ H Cl 3.16 CH₃ CH₃ H 2 COC₂H₅ H Cl 3.17 CH₃ CH₃ H 0 COiPr H Cl 3.18 CH₃ CH₃ H 2 COiPr H Cl 3.19 C₂H₅ H H 0 COCH₃ H Cl 3.20 C₂H₅ H H 2 COCH₃ H Cl 3.21 C₂H₅ H H 0 COC₂H₅ H Cl 3.22 C₂H₅ H H 2 COC₂H₅ H Cl 3.23 C₂H₅ H H 0 COiPr H Cl 3.24 C₂H₅ H H 2 COiPr H Cl

TABLE 4 Compounds of the formula

No. R¹⁵ R¹⁶ R¹⁷ n X Y M L 4.1 CH₃ CH₃ H 0 CH₂ C═O H CH₃ 4.2 CH₃ CH₃ H 2 CH₂ C═O H CH₃ 4.3 CH₃ CH₃ H 0 CH₂ CHOCH₃ H CH₃ 4.4 CH₃ CH₃ H 2 CH₂ CHOCH₃ H CH₃ 4.5 CH₃ CH₃ H 0 CH₂ CHOC₂H₅ H CH₃ 4.6 CH₃ CH₃ H 2 CH₂ CHOC₂H₅ H CH₃ 4.7 CH₃ CH₃ H 0 CH₂ CHOiPr H CH₃ 4.8 CH₃ CH₃ H 2 CH₂ CHOiPr H CH₃ 4.9 CH₃ CH₃ H 0 CH₂ CHOH H CH₃ 4.10 CH₃ CH₃ H 2 CH₂ CHOH H CH₃ 4.11 CH₃ CH₃ H 0 CH₂ C═NOCH₃ H CH₃ 4.12 CH₃ CH₃ H 2 CH₂ C═NOCH₃ H CH₃ 4.13 CH₃ CH₃ H 0 CH₂ C═NOC₂H₅ H CH₃ 4.14 CH₃ CH₃ H 2 CH₂ C═NOC₂H₅ H CH₃ 4.15 CH₃ CH₃ H 0 CH₂ C═NOiPr H CH₃ 4.16 CH₃ CH₃ H 2 CH₂ C═NOiPr H CH₃ 4.17 CH₃ CH₃ H 0 CH₂ C═NOCH₂CH═CHCl H CH₃ 4.18 CH₃ CH₃ H 2 CH₂ C═NOCH₂CH═CHCl H CH₃ 4.19 CH₃ CH₃ H 0 CH₂ C═NOCH₂C₆H₅ H CH₃ 4.20 CH₃ CH₃ H 2 CH₂ C═NOCH₂C₆H₅ H CH₃ 4.21 CH₃ CH₃ H 0 CH₂ C(CH₃)₂ H CH₃ 4.22 CH₃ CH₃ H 2 CH₂ C(CH₃)₂ H CH₃ 4.23 C₂H₅ H H 0 CH₂ C═O H CH₃ 4.24 C₂H₅ H H 2 CH₂ C═O H CH₃ 4.25 C₂H₅ H H 0 CH₂ CHOCH₃ H CH₃ 4.26 C₂H₅ H H 2 CH₂ CHOCH₃ H CH₃ 4.27 C₂H₅ H H 0 CH₂ CHOC₂H₅ H CH₃ 4.28 C₂H₅ H H 2 CH₂ CHOC₂H₅ H CH₃ 4.29 C₂H₅ H H 0 CH₂ CHOiPr H CH₃ 4.30 C₂H₅ H H 2 CH₂ CHOiPr H CH₃ 4.31 C₂H₅ H H 0 CH₂ CHOH H CH₃ 4.32 C₂H₅ H H 2 CH₂ CHOH H CH₃ 4.33 C₂H₅ H H 0 CH₂ C═NOCH₃ H CH₃ 4.34 C₂H₅ H H 2 CH₂ C═NOCH₃ H CH₃ 4.35 C₂H₅ H H 0 CH₂ C═NOC₂H₅ H CH₃ 4.36 C₂H₅ H H 2 CH₂ C═NOC₂H₅ H CH₃ 4.37 C₂H₅ H H 0 CH₂ C═NOiPr H CH₃ 4.38 C₂H₅ H H 2 CH₂ C═NOiPr H CH₃ 4.39 C₂H₅ H H 0 CH₂ C═NOCH₂CH═CHCl H CH₃ 4.40 C₂H₅ H H 2 CH₂ C═NOCH₂CH═CHCl H CH₃ 4.41 C₂H₅ H H 0 CH₂ C═NOCH₂C₆H₅ H CH₃ 4.42 C₂H₅ H H 2 CH₂ C═NOCH₂C₆H₅ H CH₃ 4.43 C₂H₅ H H 0 CH₂ C(CH₃)₂ H CH₃ 4.44 C₂H₅ H H 2 CH₂ C(CH₃)₂ H CH₃ 4.45 CH₃ CH₃ H 0 CH₂ C═O H Cl 4.46 CH₃ CH₃ H 2 CH₂ C═O H Cl 4.47 CH₃ CH₃ H 0 CH₂ CHOCH₃ H Cl 4.48 CH₃ CH₃ H 2 CH₂ CHOCH₃ H Cl 4.49 CH₃ CH₃ H 0 CH₂ CHOC₂H₅ H Cl 4.50 CH₃ CH₃ H 2 CH₂ CHOC₂H₅ H CI 4.51 CH₃ CH₃ H 0 CH₂ CHOiPr H Cl 4.52 CH₃ CH₃ H 2 CH₂ CHOiPr H Cl 4.53 CH₃ CH₃ H 0 CH₂ CHOH H Cl 4.54 CH₃ CH₃ H 2 CH₂ CHOH H Cl 4.55 CH₃ CH₃ H 0 CH₂ C═NOCH₃ H Cl 4.56 CH₃ CH₃ H 2 CH₂ C═NOCH₃ H Cl 4.57 CH₃ CH₃ H 0 CH₂ C═NOC₂H₅ H Cl 4.58 CH₃ CH₃ H 2 CH₂ C═NOC₂H₅ H Cl 4.59 CH₃ CH₃ H 0 CH₂ C═NOiPr H Cl 4.60 CH₃ CH₃ H 2 CH₂ C═NOiPr H Cl 4.61 CH₃ CH₃ H 0 CH₂ C═NOCH₂CH═CHCl H Cl 4.62 CH₃ CH₃ H 2 CH₂ C═NOCH₂CH═CHCl H Cl 4.63 CH₃ CH₃ H 0 CH₂ C═NOCH₂C₆H₅ H Cl 4.64 CH₃ CH₃ H 2 CH₂ C═NOCH₂C₆H₅ H Cl 4.65 CH₃ CH₃ H 0 CH₂ C(CH₃)₂ H Cl 4.66 CH₃ CH₃ H 2 CH₂ C(CH₃)₂ H Cl 4.67 C₂H₅ H H 0 CH₂ C═O H Cl 4.68 C₂H₅ H H 2 CH₂ C═O H Cl 4.69 C₂H₅ H H 0 CH₂ CHOCH₃ H Cl 4.70 C₂H₅ H H 2 CH₂ CHOCH₃ H Cl 4.71 C₂H₅ H H 0 CH₂ CHOC₂H₅ H Cl 4.72 C₂H₅ H H 2 CH₂ CHOC₂H₅ H Cl 4.73 C₂H₅ H H 0 CH₂ CHOiPr H Cl 4.74 C₂H₅ H H 2 CH₂ CHOiPr H Cl 4.75 C₂H₅ H H 0 CH₂ CHOH H Cl 4.76 C₂H₅ H H 2 CH₂ CHOH H Cl 4.77 C₂H₅ H H 0 CH₂ C═NOCH₃ H Cl 4.78 C₂H₅ H H 2 CH₂ C═NOCH₃ H Cl 4.79 C₂H₅ H H 0 CH₂ C═NOC₂H₅ H Cl 4.80 C₂H₅ H H 2 CH₂ C═NOC₂H₅ H Cl 4.81 C₂H₅ H H 0 CH₂ C═NOiPr H Cl 4.82 C₂H₅ H H 2 CH₂ C═NOiPr H Cl 4.83 C₂H₅ H H 0 CH₂ C═NOCH₂CH═CHCl H Cl 4.84 C₂H₅ H H 2 CH₂ C═NOCH₂CH═CHCl H Cl 4.85 C₂H₅ H H 0 CH₂ C═NOCH₂C₆H₅ H Cl 4.86 C₂H₅ H H 2 CH₂ C═NOCH₂C₆H₅ H Cl 4.87 C₂H₅ H H 0 CH₂ C(CH₃)₂ H Cl 4.88 C₂H₅ H H 2 CH₂ C(CH₃)₂ H Cl 4.89 CH₃ CH₃ H 0 (CH₂)₂ C═O H Cl 4.90 CH₃ CH₃ H 2 (CH₂)₂ C═O H Cl 4.91 CH₃ CH₃ H 0 (CH₂)₂ CHOCH₃ H Cl 4.92 CH₃ CH₃ H 2 (CH₂)₂ CHOCH₃ H Cl 4.93 CH₃ CH₃ H 0 (CH₂)₂ CHOC₂H₅ H Cl 4.94 CH₃ CH₃ H 2 (CH₂)₂ CHOC₂H₅ H Cl 4.95 CH₃ CH₃ H 0 (CH₂)₂ CHOiPr H Cl 4.96 CH₃ CH₃ H 2 (CH₂)₂ CHOiPr H Cl 4.97 CH₃ CH₃ H 0 (CH₂)₂ CHOH H Cl 4.98 CH₃ CH₃ H 2 (CH₂)₂ CHOH H ci 4.99 CH₃ CH₃ H 0 (CH₂)₂ C═NOCH₃ H Cl 4.100 CH₃ CH₃ H 2 (CH₂)₂ C═NOCH₃ H Cl 4.101 CH₃ CH₃ H 0 (CH₂)₂ C═NOC₂H₅ H Cl 4.102 CH₃ CH₃ H 2 (CH₂)₂ C═NOC₂H₅ H Cl 4.103 CH₃ CH₃ H 0 (CH₂)₂ C═NOiPr H Cl 4.104 CH₃ CH₃ H 2 (CH₂)₂ C═NOiPr H Cl 4.105 CH₃ CH₃ H 0 (CH₂)₂ C═NOCH₂CH═CHCl H Cl 4.106 CH₃ CH₃ H 2 (CH₂)₂ C═NOCH₂CH═CHCl H Cl 4.107 CH₃ CH₃ H 0 (CH₂)₂ C═NOCH₂C₆H₅ H Cl 4.108 CH₃ CH₃ H 2 (CH₂)₂ C═NOCH₂C₆H₅ H Cl 4.109 CH₃ CH₃ H 0 (CH₂)₂ C(CH₃)₂ H Cl 4.110 CH₃ CH₃ H 2 (CH₂)₂ C(CH₃)₂ H Cl 4.111 C₂H₅ H H 0 (CH₂)₂ C═O H Cl 4.112 C₂H₅ H H 2 (CH₂)₂ C═O H Cl 4.113 C₂H₅ H H 0 (CH₂)₂ CHOCH₃ H Cl 4.114 C₂H₅ H H 2 (CH₂)₂ CHOCH₃ H Cl 4.115 C₂H₅ H H 0 (CH₂)₂ CHOC₂H₅ H Cl 4.116 C₂H₅ H H 2 (CH₂)₂ CHOC₂H₅ H Cl 4.117 C₂H₅ H H 0 (CH₂)₂ CHOiPr H Cl 4.118 C₂H₅ H H 2 (CH₂)₂ CHOiPr H Cl 4.119 C₂H₅ H H 0 (CH₂)₂ CHOH H Cl 4.120 C₂H₅ H H 2 (CH₂)₂ CHOH H Cl 4.121 C₂H₅ H H 0 (CH₂)₂ C═NOCH₃ H Cl 4.122 C₂H₅ H H 2 (CH₂)₂ C═NOCH₃ H Cl 4.123 C₂H₅ H H 0 (CH₂)₂ C═NOC₂H₅ H Cl 4.124 C₂H₅ H H 2 (CH₂)₂ C═NOC₂H₅ H C1 4.125 C₂H₅ H H 0 (CH₂)₂ C═NOiPr H Cl 4.126 C₂H₅ H H 2 (CH₂)₂ C═NOiPr H Cl 4.127 C₂H₅ H H 0 (CH₂)₂ C═NOCH₂CH═CHCl H Cl 4.128 C₂H₅ H H 2 (CH₂)₂ C═NOCH₂CH═CHCl H Cl 4.129 C₂H₅ H H 0 (CH₂)₂ C═NOCH₂C₆H₅ H Cl 4.130 C₂H₅ H H 2 (CH₂)₂ C═NOCH₂C₆H₅ H Cl 4.131 C₂H₅ H H 0 (CH₂)₂ C(CH₃)₂ H Cl 4.132 C₂H₅ H H 2 (CH₂)₂ C(CH₃)₂ H Cl 4.133 CH₃ CH₃ H 0 (CH₂)₂ C═O H CH₃ 4.134 CH₃ CH₃ H 2 (CH₂)₂ C═O H CH₃ 4.135 CH₃ CH₃ H 0 (CH₂)₂ CHOCH₃ H CH₃ 4.136 CH₃ CH₃ H 2 (CH₂)₂ CHOCH₃ H CH₃ 4.137 CH₃ CH₃ H 0 (CH₂)₂ CHOC₂H₅ H CH₃ 4.138 CH₃ CH₃ H 2 (CH₂)₂ CHOC₂H₅ H CH₃ 4.139 CH₃ CH₃ H 0 (CH₂)₂ CHOiPr H CH₃ 4.140 CH₃ CH₃ H 2 (CH₂)₂ CHOiPr H CH₃ 4.141 CH₃ CH₃ H 0 (CH₂)₂ CHOH H CH₃ 4.142 CH₃ CH₃ H 2 (CH₂)₂ CHOH H CH₃ 4.143 CH₃ CH₃ H 0 (CH₂)₂ C═NOCH₃ H CH₃ 4.144 CH₃ CH₃ H 2 (CH₂)₂ C═NOCH₃ H CH₃ 4.145 CH₃ CH₃ H 0 (CH₂)₂ C═NOC₂H₅ H CH₃ 4.146 CH₃ CH₃ H 2 (CH₂)₂ C═NOC₂H₅ H CH₃ 4.147 CH₃ CH₃ H 0 (CH₂)₂ C═NOiPr H CH₃ 4.148 CH₃ CH₃ H 2 (CH₂)₂ C═NOiPr H CH₃ 4.149 CH₃ CH₃ H 0 (CH₂)₂ C═NOCH₂CH═CHCl H CH₃ 4.150 CH₃ CH₃ H 2 (CH₂)₂ C═NOCH₂CH═CHCl H CH₃ 4.151 CH₃ CH₃ H 0 (CH₂)₂ C═NOCH₂C₆H₅ H CH₃ 4.152 CH₃ CH₃ H 2 (CH₂)₂ C═NOCH₂C₆H₅ H CH₃ 4.153 CH₃ CH₃ H 0 (CH₂)₂ C(CH₃)₂ H CH₃ 4.154 CH₃ CH₃ H 2 (CH₂)₂ C(CH₃)₂ H CH₃ 4.155 C₂H₅ H H 0 (CH₂)₂ C═O H CH₃ 4.156 C₂H₅ H H 2 (CH₂)₂ C═O H CH₃ 4.157 C₂H₅ H H 0 (CH₂)₂ CHOCH₃ H CH₃ 4.158 C₂H₅ H H 2 (CH₂)₂ CHOCH₃ H CH₃ 4.159 C₂H₅ H H 0 (CH₂)₂ CHOC₂H₅ H CH₃ 4.160 C₂H₅ H H 2 (CH₂)₂ CHOC₂H₅ H. CH₃ 4.161 C₂H₅ H H 0 (CH₂)₂ CHOiPr H CH₃ 4.162 C₂H₅ H H 2 (CH₂)₂ CHOiPr H CH₃ 4.163 C₂H₅ H H 0 (CH₂)₂ CHOH H CH₃ 4.164 C₂H₅ H H 2 (CH₂)₂ CHOH H CH₃ 4.165 C₂H₅ H H 0 (CH₂)₂ C═NOCH₃ H CH₃ 4.166 C₂H₅ H H 2 (CH₂)₂ C═NOCH₃ H CH₃ 4.167 C₂H₅ H H 0 (CH₂)₂ C═NOC₂H₅ H CH₃ 4.168 C₂H₅ H H 2 (CH₂)₂ C═NOC₂H₅ H CH₃ 4.169 C₂H₅ H H 0 (CH₂)₂ C═NOiPr H CH₃ 4.170 C₂H₅ H H 2 (CH₂)₂ C═NOiPr H CH₃ 4.171 C₂H₅ H H 0 (CH₂)₂ C═NOCH₂CH═CHCl H CH₃ 4.172 C₂H₅ H H 2 (CH₂)₂ C═NOCH₂CH═CHCl H CH₃ 4.173 C₂H₅ H H 0 (CH₂)₂ C═NOCH₂C₆H₅ H CH₃ 4.174 C₂H₅ H H 2 (CH₂)₂ C═NOCH₂C₆H₅ H CH₃ 4.175 C₂H₅ H H 0 (CH₂)₂ C(CH₃)₂ H CH₃ 4.176 C₂H₅ H H 2 (CH₂)₂ C(CH₃)₂ H CH₃ 4.177 CH₃ CH₃ p-CH₃—C₆H₄—SO₂— 0 (CH₂)₂ C═O H CH₃ 4.178 CH₃ CH₃ p-CH₃—C₆H₄—SO₂— 2 (CH₂)₂ C═O H CH₃ 4.179 CH₃ CH₃ p-CH₃—C₆H₄—SO₂— 0 (CH₂)₂ CHOCH₃ H CH₃ 4.180 CH₃ CH₃ p-CH₃—C₆H₄—SO₂— 2 (CH₂)₂ CHOCH₃ H CH₃ 4.181 CH₃ CH₃ p-CH₃—C₆H₄—SO₂— 0 (CH₂)₂ CHOC₂H₅ H CH₃ 4.182 CH₃ CH₃ p-CH₃—C₆H₄—SO₂— 2 (CH₂)₂ CHOC₂H₅ H CH₃ 4.183 CH₃ CH₃ p-CH₃—C₆H₄—SO₂— 0 (CH₂)₂ CHOiPr H CH₃ 4.184 CH₃ CH₃ p-CH₃—C₆H₄—SO₂— 2 (CH₂)₂ CHOiPr H CH₃ 4.185 CH₃ CH₃ p-CH₃—C₆H₄—SO₂— 0 (CH₂)₂ CHOH H CH₃ 4.186 CH₃ CH₃ p-CH₃—C₆H₄—SO₂— 2 (CH₂)₂ CHOH H CH₃ 4.187 CH₃ CH₃ p-CH₃—C₆H₄—SO₂— 0 (CH₂)₂ C═NOCH₃ H CH₃ 4.188 CH₃ CH₃ p-CH₃—C₆H₄—SO₂— 2 (CH₂)₂ C═NOCH₃ H CH₃ 4.189 CH₃ CH₃ p-CH₃—C₆H₄—SO₂— 0 (CH₂)₂ C═NOC₂H₅ H CH₃ 4.190 CH₃ CH₃ p-CH₃—C₆H₄—SO₂— 2 (CH₂)₂ C═NOC₂H₅ H CH₃ 4.191 CH₃ CH₃ p-CH₃—C₆H₄—SO₂— 0 (CH₂)₂ C═NOiPr H CH₃ 4.192 CH₃ CH₃ p-CH₃—C₆H₄—SO₂— 2 (CH₂)₂ C═NOiPr H CH₃ 4.193 CH₃ CH₃ p-CH₃—C₆H₄—SO₂— 0 (CH₂)₂ C═NOCH₂CH═CHCl H CH₃ 4.194 CH₃ CH₃ p-CH₃—C₆H₄—SO₂— 2 (CH₂)₂ C═NOCH₂CH═CHCl H CH₃ 4.195 CH₃ CH₃ p-CH₃—C₆H₄—SO₂— 0 (CH₂)₂ C═NOCH₂C₆H₅ H CH₃ 4.196 CH₃ CH₃ p-CH₃—C₆H₄—SO₂— 2 (CH₂)₂ C═NOCH₂C₆H₅ H CH₃ 4.197 CH₃ CH₃ p-CH₃—C₆H₄—SO₂— 0 (CH₂)₂ C(CH₃)₂ H CH₃ 4.198 CH₃ CH₃ p-CH₃—C₆H₄—SO₂— 2 (CH₂)₂ C(CH₃)₂ H CH₃ 4.199 C₂H₅ H p-CH₃—C₆H₄—SO₂— 0 (CH₂)₂ C═O H CH₃ 4.200 C₂H₅ H p-CH₃—C₆H₄—SO₂— 2 (CH₂)₂ C═O H CH₃ 4.201 C₂H₅ H p-CH₃—C₆H₄—SO₂— 0 (CH₂)₂ CHOCH₃ H CH₃ 4.202 C₂H₅ H p-CH₃—C₆H₄—SO₂— 2 (CH₂)₂ CHOCH₃ H CH₃ 4.203 C₂H₅ H p-CH₃—C₆H₄—SO₂— 0 (CH₂)₂ CHOC₂H₅ H CH₃ 4.204 C₂H₅ H p-CH₃—C₆H₄—SO₂— 2 (CH₂)₂ CHOC₂H₅ H CH₃ 4.205 C₂H₅ H p-CH₃—C₆H₄—SO₂— 0 (CH₂)₂ CHOiPr H CH₃ 4.206 C₂H₅ H p-CH₃—C₆H₄—SO₂— 2 (CH₂)₂ CHOiPr H CH₃ 4.207 C₂H₅ H p-CH₃—C₆H₄—SO₂— 0 (CH₂)₂ CHOH H CH₃ 4.208 C₂H₅ H p-CH₃—C₆H₄—SO₂— 2 (CH₂)₂ CHOH H CH₃ 4.209 C₂H₅ H p-CH₃—C₆H₄—SO₂— 0 (CH₂)₂ C═NOCH₃ H CH₃ 4.210 C₂H₅ H p-CH₃—C₆H₄—SO₂— 2 (CH₂)₂ C═NOCH₃ H CH₃ 4.211 C₂H₅ H p-CH₃—C₆H₄—SO₂— 0 (CH₂)₂ C═NOC₂H₅ H CH₃ 4.212 C₂H₅ H p-CH₃—C₆H₄—SO₂— 2 (CH₂)₂ C═NOC₂H₅ H CH₃ 4.213 C₂H₅ H p-CH₃—C₆H₄—SO₂— 0 (CH₂)₂ C═NOiPr H CH₃ 4.214 C₂H₅ H p-CH₃—C₆H₄—SO₂— 2 (CH₂)₂ C═NOiPr H CH₃ 4.215 C₂H₅ H p-CH₃—C₆H₄—SO₂— 0 (CH₂)₂ C═NOCH₂CH═CHCl H CH₃ 4.216 C₂H₅ H p-CH₃—C₆H₄—SO₂— 2 (CH₂)₂ C═NOCH₂CH═CHCl H CH₃ 4.217 C₂H₅ H p-CH₃—C₆H₄—SO₂— 0 (CH₂)₂ C═NOCH₂C₆H₅ H CH₃ 4.218 C₂H₅ H p-CH₃—C₆H₄—SO₂— 2 (CH₂)₂ C═NOCH₂C₆H₅ H CH₃ 4.219 C₂H₅ H p-CH₃—C₆H₄—SO₂— 0 (CH₂)₂ C(CH₃)₂ H CH₃ 4.220 C₂H₅ H p-CH₃—C₆H₄—SO₂— 2 (CH₂)₂ C(CH₃)₂ H CH₃ 4.221 CH₃ CH₃ H 0 (CH₂)₂ CH—NHCH₃ H CH₃ 4.222 CH₃ CH₃ H 2 (CH₂)₂ CH—NHCH₃ H CH₃ 4.223 CH₃ CH₃ H 0 (CH₂)₂ CH—NHC₂H₅ H CH₃ 4.224 CH₃ CH₃ H 2 (CH₂)₂ CH—NHC₂H₅ H CH₃ 4.225 CH₃ CH₃ H 0 (CH₂)₂ CH—N(CH₃)₂ H CH₃ 4.226 CH₃ CH₃ H 2 (CH₂)₂ CH—N(CH₃)₂ H CH₃ 4.227 CH₃ CH₃ H 0 (CH₂)₂ CH—NHOC₂H₅ H CH₃ 4.228 CH₃ CH₃ H 2 (CH₂)₂ CH—NHOC₂H₅ H CH₃ 4.229 CH₃ CH₃ H 0 (CH₂)₂ CH—N(CH₃)OC₂H₅ H CH₃ 4.230 CH₃ CH₃ H 2 (CH₂)₂ CH—N(CH₃)OC₂H₅ H CH₃ 4.231 CH₃ CH₃ H 0 (CH₂)₂ C═N—NH₂ H CH₃ 4.232 CH₃ CH₃ H 2 (CH₂)₂ C═N—NH₂ H CH₃ 4.233 CH₃ CH₃ H 0 (CH₂)₂ C═N—N(CH₃)₂ H CH₃ 4.234 CH₃ CH₃ H 2 (CH₂)₂ C═N—N(CH₃)₂ H CH₃ 4.235 CH₃ CH₃ H 0 (CH₂)₂ C(CH₃)—OCH₃ H CH₃ 4.236 CH₃ CH₃ H 2 (CH₂)₂ C(CH₃)—OCH₃ H CH₃ 4.237 CH₃ CH₃ H 0 (CH₂)₂ O H CH₃ 4.238 CH₃ CH₃ H 2 (CH₂)₂ O H CH₃ 4.239 C₂H₅ H H 0 (CH₂)₂ CH—NHCH₃ H CH₃ 4.240 C₂H₅ H H 2 (CH₂)₂ CH—NHCH₃ H CH₃ 4.241 C₂H₅ H H 0 (CH₂)₂ CH—NHC₂H₅ H CH₃ 4.242 C₂H₅ H H 2 (CH₂)₂ CH—NHC₂H₅ H CH₃ 4.243 C₂H₅ H H 0 (CH₂)₂ CH—N(CH₃)₂ H CH₃ 4.244 C₂H₅ H H 2 (CH₂)₂ CH—N(CH₃)₂ H CH₃ 4.245 C₂H₅ H H 0 (CH₂)₂ CH—NHOC₂H₅ H CH₃ 4.246 C₂H₅ H H 2 (CH₂)₂ CH—NHOC₂H₅ H CH₃ 4.247 C₂H₅ H H 0 (CH₂)₂ CH—N(CH₃)OC₂H₅ H CH₃ 4.248 C₂H₅ H H 2 (CH₂)₂ CH—N(CH₃)OC₂H₅ H CH₃ 4.249 C₂H₅ H H 0 (CH₂)₂ C═N—NH₂ H CH₃ 4.250 C₂H₅ H H 2 (CH₂)₂ C═N—NH₂ H CH₃ 4.251 C₂H₅ H H 0 (CH₂)₂ C═N—N(CH₃)₂ H CH₃ 4.252 C₂H₅ H H 2 (CH₂)₂ C═N—N(CH₃)₂ H CH₃ 4.253 C₂H₅ H H 0 (CH₂)₂ C(CH₃)—OCH₃ H CH₃ 4.254 C₂H₅ H H 2 (CH₂)₂ C(CH₃)—OCH₃ H CH₃ 4.255 C₂H₅ H H 0 (CH₂)₂ O H CH₃ 4.256 C₂H₅ H H 2 (CH₂)₂ O H CH₃ 4.257 CH₃ CH₃ H 0 (CH₂)₂ CH—NHCH₃ H Cl 4.258 CH₃ CH₃ H 2 (CH₂)₂ CH—NHCH₃ H Cl 4.259 CH₃ CH₃ H 0 (CH₂)₂ CH—NHC₂H₅ H Cl 4.260 CH₃ CH₃ H 2 (CH₂)₂ CH—NHC₂H₅ H Cl 4.261 CH₃ CH₃ H 0 (CH₂)₂ CH—N(CH₃)₂ H Cl 4.262 CH₃ CH₃ H 2 (CH₂)₂ CH—N(CH₃)₂ H Cl 4.263 CH₃ CH₃ H 0 (CH₂)₂ CH—NHOC₂H₅ H Cl 4.264 CH₃ CH₃ H 2 (CH₂)₂ CH—NHOC₂H₅ H Cl 4.265 CH₃ CH₃ H 0 (CH₂)₂ CH—N(CH₃)OC₂H₅ H Cl 4.266 CH₃ CH₃ H 2 (CH₂)₂ CH—N(CH₃)OC₂H₅ H Cl 4.267 CH₃ CH₃ H 0 (CH₂)₂ C═N—NH₂ H Cl 4.268 CH₃ CH₃ H 2 (CH₂)₂ C═N—NH₂ H Cl 4.269 CH₃ CH₃ H 0 (CH₂)₂ C═N—N(CH₃)₂ H Cl 4.270 CH₃ CH₃ H 2 (CH₂)₂ C═N—N(CH₃)₂ H Cl 4.271 CH₃ CH₃ H 0 (CH₂)₂ C(CH₃)—OCH₃ H Cl 4.272 CH₃ CH₃ H 2 (CH₂)₂ C(CH₃)—OCH₃ H Cl 4.273 CH₃ CH₃ H 0 (CH₂)₂ O H Cl 4.274 CH₃ CH₃ H 2 (CH₂)₂ O H Cl 4.275 C₂H₅ H H 0 (CH₂)₂ CH—NHCH₃ H Cl 4.276 C₂H₅ H H 2 (CH₂)₂ CH—NHCH₃ H Cl 4.277 C₂H₅ H H 0 (CH₂)₂ CH—NHC₂H₅ H Cl 4.278 C₂H₅ H H 2 (CH₂)₂ CH—NHC₂H₅ H Cl 4.279 C₂H₅ H H 0 (CH₂)₂ CH—N(CH₃)₂ H Cl 4.280 C₂H₅ H H 2 (CH₂)₂ CH—N(CH₃)₂ H Cl 4.281 C₂H₅ H H 0 (CH₂)₂ CH—NHOC₂H₅ H Cl 4.282 C₂H₅ H H 2 (CH₂)₂ CH—NHOC₂H₅ H Cl 4.283 C₂H₅ H H 0 (CH₂)₂ CH—N(CH₃)OC₂H₅ H Cl 4.284 C₂H₅ H H 2 (CH₂)₂ CH—N(CH₃)OC₂H₅ H Cl 4.285 C₂H₅ H H 0 (CH₂)₂ C═N—NH₂ H Cl 4.286 C₂H₅ H H 2 (CH₂)₂ C═N—NH₂ H Cl 4.287 C₂H₅ H H 0 (CH₂)₂ C═N—N(CH₃)₂ H Cl 4.288 C₂H₅ H H 2 (CH₂)₂ C═N—N(CH₃)₂ H Cl 4.289 C₂H₅ H H 0 (CH₂)₂ C(CH₃)—OCH₃ H Cl 4.290 C₂H₅ H H 2 (CH₂)₂ C(CH₃)—OCH₃ H Cl 4.291 C₂H₅ H H 0 (CH₂)₂ O H Cl 4.292 C₂H₅ H H 2 (CH₂)₂ O H Cl

PREPARATION EXAMPLES A) Preparation of the Starting Materials and Intermediates

1. 3-Thio-2-methylbenzoic acid

100 g (0.66 mol) of 3-amino-2-methylbenzoic acid together with 270 g of ice and 127 ml of concentrated HCl are introduced into the reaction vessel. 45.7 g (0.66 mol) of sodium nitrite in 270 ml of water are then added dropwise at 0-10° C.

In a second vessel, 84.2 g (0.79 mol) of sodium carbonate and 106 g (0.66 mol) of potassium methyl xanthogenate are dissolved in 450 ml of water, and the solution was heated at 60-70° C. The diazonium solution is carefully added dropwise. Stirring is continued for 1 hour. 106 g (2.65 mol) of sodium hydroxide in 270 ml of water are subsequently added, the solution is stirred for a further 2 hours and acidified using hydrochloric acid, and the precipitate which forms is filtered off with suction. The solid is washed with water and dried.

Yield: 110 g (100% of theory) of 3-thio-2-methylbenzoic acid; melting point: 155° C.; ¹H NMR (d⁶-DMSO): δ [ppm]=13.0 (1H, bs), 7.7 (2H, m), 7.3 (1H, tr), 2.4 (3H, s).

2. Methyl 3-thio-2-methylbenzoate

110 g (0.66 mol) of 3-thio-2-methylbenzoate are dissolved in 1.6 l of methanol containing 5% of sulfuric acid, and the mixture is refluxed for 5 hours. The alcohol is subsequently distilled off, the residue is taken up in ethyl acetate, and the organic phase is washed with water and sodium carbonate solution, dried using sodium sulfate and evaporated on a rotary evaporator.

Yield: 104 g (87% of theory) of methyl 3-thio-2-methyl-benzoate; ¹H NMR (CDCl₃): δ [ppm]=7.6 (1H, d), 7.4 (1H, d), 7.1 (1H, d), 3.9 (3H, s), 3.4 (1H, s), 2.5 (3H, s).

3. Methyl 3-carboxyethylthio-2-methylbenzoate

70 g (0.38 mol) of methyl 3-thio-2-methylbenzoate are dissolved in 400 ml of water and refluxed for 7 hours together with 30.8 g (0.77 mol) of sodium hydroxide solution and 58.8 g (0.45 mol) of bromopropionic acid. After cooling, the aqueous phase is washed using methyl tert-butyl ether. The aqueous phase is subsequently acidified using 2N HCl, the precipitate which has formed is filtered off with suction and washed with water, and the product is dried.

Yield: 75.5 g (78% of theory) of methyl 2-methyl-3-carboxyethylthiobenzoate; ¹H NMR (CDCl₃): δ [ppm]=7.66 (1H, d), 7.51 (1H, d), 7.20 (1H, tr), 3.96 (3H, s), 3.18 (2H, tr), 2.70 (2H, tr), 2.63 (3H, s).

4. Methyl 8-methylthiochroman-4-one-7-carboxylate

4 g (15.8 mmol) of methyl 2-methyl-3-carboxyethylthiobenzoate are stirred for 15 minutes in 40 g of polyphosphoric acid at 70° C. The reaction solution is then poured into ice-water and the precipitate which has formed is filtered off with suction. The product is washed with water and dried in a drying oven. The cyclization may give methyl 8-methylthiochromen-4-onecarboxylate, which can be removed by chromatography.

Yield: 3.1 g (83% of theory) of methyl 8-methylthiochroman-4-one-7-carboxylate; ¹H NMR (CDCl₃): δ [ppm]=8.00 (1H, d), 7.30 (1H, d), 3.94 (3H, s), 3.15 (2H, m), 2.98 (2H, m), 2.50 (3H, s);

Secondary Product

Methyl 8-methylthiochromen-4-onecarboxylate: ¹H NMR (CDCl₃): δ [ppm]=8.4 (1H, d), 7.9 (1H, d), 7.8 (1H, d), 7.0 (1H, d), 4.0 (3H, s), 2.7 (3H, s).

5. 8-Methylthiochroman-4-one-7-carboxylic acid

41.1 g (0.17 mol) of methyl 8-methyl thiochroman-4-one-7-carboxylate are hydrolyzed at reflux temperature in a mixture of 400 ml of water and methanol using 10.3 g (0.26 mol) of NaOH. The methanol is subsequently distilled off, and the residue is diluted with water and acidified with 2N hydrochloric acid. The product of interest precipitates and is filtered off with suction, washed with water and dried.

Yield: 34.4 g (89% of theory) of 8-methylthiochroman-4-one-7-carboxylic acid; melting point: 243-246° C.

6. 8-Methyl-1,1-dioxothiochroman-4-one-7-carboxylic acid

20 g (0.09 mol) of 8-methylthiochroman-4-one-7-carboxylic acid are dissolved in 100 ml of acetic acid. One spatula-tip full of sodium tungstate is added. 24.9 g (0.22 mol) of 30% strength hydrogen peroxide solution are then added dropwise at 50° C. Stirring is continued for one hour at RT. The reaction solution is then poured into water, during which process a precipitate is formed, which is filtered off with suction. The product is washed with water and then dried.

Yield: 18.4 g (80% of theory) of 8-methyl-1,1-dioxothiochroman-4-one-7-carboxylic acid; melting point: 224-225° C.

7. Methyl 4-hydroxy-8-methylthiochromane-7-carboxylate

30 g (0.127 mol) of methyl 8-methylthiochroman-4-one-7-carboxylate are dissolved in a mixture of 120 ml of methylene chloride and 60 ml of methanol and the solution is cooled to 0-5° C. 2.4 g (0.064 mol) of sodium borohydride are then added a little at a time. Stirring is continued at this temperature for one hour. 200 ml of 2N hydrochloric acid are added to the reaction solution. This gives two phases. The organic phase is separated off and dried and the solvent is distilled off. The crude product is further reacted directly without further purification.

Yield: 27.6 g (91% of theory) of methyl 4-hydroxy-8-methylthiochromane-7-carboxylate.

8. Methyl 4-ethoxy-8-methylthiochromane-7-carboxylate

13.8 g (0.058 mol) of methyl 4-hydroxy-8-methylthiochromane-7-carboxylate are heated below boiling point for 4 hours in 60 ml of ethanol with 1 g of sulfuric acid added. The solvent is then distilled off and the residue is taken up in water. The aqueous phase is extracted using ethyl acetate. The organic phase is washed using sodium hydrogen carbonate solution, dried and concentrated. The product is purified by chromatography.

Yield: 10.1 g (60% of theory) of methyl 4-ethoxy-8-methylthiochromane-7-carboxylate; ¹H NMR (CDCl₃): δ [ppm] =7.44 (1H, d), 7.13 (1H, d), 4.40 (1H, m), 3.90 (3H, s), 3.60 (2H, m), 3.38 (1 H, dtr), 2.90 (1H, m), 2.50 (3H, s), 2.40 (1H, m ), 1.98 (1H, m) 1.10 (3H, tr).

Methyl 4-methoxy-8-methylthiochroman-4-one-7-carboxylate and methyl 4-isopropoxy-8-methylthiochroman-4-one-7-carboxylate are obtained by a reaction similar to the above protocol, but methanol was substituted for ethanol in the case of methyl 4-methoxy-8-methylthiochroman-4-one-7-carboxylate and isopropanol for ethanol in the case of methyl 4-isopropoxy-8-methylthiochroman-4-one-7-carboxylate.

9 . 4-Ethoxy-8-methylthiochromane-7-carboxylic acid

2.1 g of sodium hydroxide solution are dissolved in 20 ml of water. Methyl 4-ethoxy-8-methylthiochroman-4-one-7-carboxylate, dissolved in 20 ml of methanol, is added dropwise at about 20° C. The mixture is refcluxed for 2 hours. The solvent is subsequently distilled off and the residue poured into 2N hydrochloric acid. The aqueous phase is extracted using methylene chloride. The organic phase is dried and concentrated.

Yield: 9.3 g (100% of theory) of 4-ethoxy-8-methyl-thiochromane-7-carboxylic acid; melting point: 89-98° C.

The hydrolysis of the corresponding esters to obtain 4-methoxy-8-methylthiochromane-7-carboxylic acid and 4-isopropoxy-8-methylthiochromane-7-carboxylic acid proceeds similarly. The same applies to the hydrolysis of the corresponding benzo(bjthiophene derivatives given below.

10. 8-Methyl-4-ethoxy-1,1-dioxothiochromane-7-carboxylic acid

8.4 g (0.033 mol) of 4-ethoxy-8-methylthiochromane-7-carboxylic acid are introduced into 60 ml of acetic acid. one spatula-tip full of sodium tungstate is added. 7.9 g (0.07 mol) of 30% strength hydrogen peroxide solution are slowly added dropwise at 50° C. Stirring is continued for 2 hours. The reaction batch is then poured into water and the aqueous phase is extracted using ethyl acetate. The organic phase is washed using bisulfite solution and then dried and concentrated.

Yield: 9.5 g (100% of theory) of 8-methyl-4-ethoxy-1,1-dioxothiochromane-7-carboxylic acid; melting point: 150° C.

11. 8-Methylthiochroman-4-one-7-carboxylic acid O-ethyloxime

0.88 g (9 mmol) of ethylhydroxylamine are introduced into 20 ml of methanol. 0.62 g (4.5 mmol) of potassium carbonate are then added. 2.0 g (9 mmol) of 8-methylthiochroman-4-one-7-carboxylic acid are subsequently added. The reaction [sic] is stirred for 10 days at about 20° C. Work-up is carried out by adding water and 2N HCl. The precipitate which forms is filtered off with suction and dried.

Yield: 2.2 g (92% of theory) of 8-methylthiochroman-4-one-7-carboxylic acid O-ethyloxime; melting point: 166° C.

12. 8-Methyl-1,1-dioxothiochroman-4-one-7-carboxylic acid O-ethyloxime

3.0 g (0.011 mol) of 8-methylthiochroman-4-one-7-carboxylic acid O-ethyloxime together with one spatula-tip full of sodium tungstate are introduced into 30 ml of acetic acid. 2.8 g (0.024 mol) of a 30% strength hydrogen peroxide solution are added dropwise at 50° C. After the reaction mixture has been stirred for one hour, it is poured into ice-water and the precipitate which forms is filtered off with suction. The product is washed with water and dried.

Yield: 2.5 g (74% of theory) of 8-methyl-1,1-dioxothiochroman-4-one-7-carboxylic acid O-ethyloxime; melting point 198° C.

13. 8-Methyl-1-oxothiochroman-4-one-7-carboxylic acid

7.0 g (31.5 mmol) of 8-methylthiochroman-4-one-7-carboxylic acid together with one spatula-tip full of sodium tungstate are introduced into 70 ml of acetic acid. 3.6 g (31.5 mmol) of a 30% strength hydrogen peroxide solution are added dropwise at 50° C. Stirring is continued for 3 hours. The reaction solution is then stirred into water. The product is extracted using ethyl acetate. The organic phase is dried and the solvent is removed. The product is purified by chromatography.

Yield: 5.4 g (72% of theory) of 8-methyl-1-oxothiochroman-4-one-7-carboxylic acid; ¹H NMR (d⁶-DMSO): δ [ppm]=8.0 (2H, m), 3.5 (3H, m), 2.8 (1H, m), 2.7 (3H,s).

14. Methyl 2-methyl-3-carboxymethylthiobenzoate

12.4 g (0.068 mol) of methyl 3-thio-2-methylbenzoate in 80 ml of dimethylformamide are added dropwise to 1.6 g (0.068 mol) of NaH in 40 ml of dimethylformamide. The mixture is stirred for 60 minutes at about 20° C. 8 g (0.068 mol) of chloroacetic acid are then added. The mixture is stirred for 4 hours at about 20° C.

Work-up is carried out by stirring the reaction mixture into ice-water/HCl.

The precipitate which forms is filtered off with suction, washed with water and dried.

Yield: 14.6 g (89% of theory) of methyl 2-methyl-3-carboxymethylthiobenzoate; ¹H NMR (d⁶-DMSO): δ [ppm]=7.55 (1H, d), 7.45 (1H, d), 7.21 (1H, tr), 3.82 (2H,s), 2.50 (3H,s).

15. Methyl 7-methylbenzo[b]thiophen-3[2H]-one-6-carboxylate

14.3 g (0.06 mmol) of 2-methyl-3-carboxymethylthiobenzoic acid are dissolved in 300 ml of methylene chloride., 13.1 g (0.11 mmol) of thionyl chloride are added dropwise. The mixture is refluxed for one hour. The solvent and excess thionyl chloride are then distilled off. The residue is taken up in 100 ml of methylene chloride and treated with 31.8 g (0.24 mmol) of aluminum trichloride. The reaction [sic] is stirred for 1 hour at about 20° C. The mixture is subsequently poured into ice-water and the organic phase is separated off. After the organic phase has been washed and dried, the solvent is removed. The product is reacted further without purification.

Yield: 12.9 g (97% of theory) of methyl 7-methyl-benzo[b]-thiophen-3[2H]-one-6-carboxylate; ¹H NMR (CDCl₃): δ [ppm]=7.65 (2H, m), 3.93 (3H, s), 3.88 (2H, s), 2.50 (3H, s).

16. Methyl 7-methyl-3-hydroxybenzo[b]thiophene-[2H]-6-carboxylate

12.8 g (0.058 mol) of 7-methyl-benzo[b]thiophen-3[2H]-one-6-carboxylate are dissolved in 120 ml of methylene chloride and 60 ml of methanol and the solution is cooled to 0° C. 1.1 g (0.029 mol) of sodium borohydride are added a little at a time. The mixture is stirred for 3 hours. The reaction is stopped by adding water. The phases are separated and the aqueous phase is extracted using methylene chloride. The combined organic phases are dried. The solvent is distilled off. The crude product is reacted further.

Yield: 13.2 g (100% of theory) of methyl 7-methyl-3-hydroxybenzo-[b]thiophene-[2H]-6-carboxylate; ¹H NMR (CDCl₃): δ [ppm] 7.6 (2H, m), 5.3 (1H, m), 3.9 (3H, s), 3.7 (1H, m), 3.3 (1H, m), 2.4 (3H, s).

17. Methyl 7-methyl-3-methoxybenzo[b]thiophene-[2H]-6-carboxylate

2.4 g (0.059 mol) of NaH is dissolved in 50 ml of DMF. 13.2 g of methyl 7-methyl-3-hydroxybenzo[b]thiophene-[2H]-6-carboxylate, dissolved in 50 ml [lacuna], are added dropwise. The mixture is subsequently stirred for 2 hours at about 20° C. 8.4 g (0.059 mol) of iodomethane are then added and the mixture is stirred for a further 2 hours.

The reaction solution is poured into ice-water and extracted using ethyl acetate. The organic phase is dried and subsequently concentrated. The product is purified by chromatography.

Yield: 3.5 g (25% of theory) of methyl 7-methyl-3-methoxybenzo[b]thiophene-[2H]-6-carboxylate; ¹H NMR (CDCl₃): δ [ppm]=7.60 (1H, d), 7.20 (1H, d), 5.04 (1H, m), 3.90 (3H, s), 3.56 (1H, m), 3.40 (3H, s), 3.38 (1H, m), 2.50 (3H, s).

The corresponding benzothiophene acids are also obtained by methods similar to the above-described hydrolysis of the thiochromanone esters.

The compounds listed in the Tables which follow are obtained in a similar manner:

TABLE 5 Intermediates of the formula

No. T n X Y L M Physical data 5.1 HO 0 (CH₂)₂ C═O H H m.p. [° C.]: 226-231 5.2 HO 2 (CH₂)₂ C═O H H m.p. [° C.]: 217-220 5.3 HO 0 (CH₂)₂ C═O H CH₃ m.p. [° C.]: 243-246 5.4 HO 2 (CH₂)₂ C═O H CH₃ m.p. [° C.]: 224-225 5.5 HO 0 (CH₂)₂ CHOCH₃ H CH₃ m.p. [° C.]: 117-118 5.6 HO 2 (CH₂)₂ CHOCH₃ H CH₃ m.p. [° C.]: 167-172 5.7 HO 0 (CH₂)₂ CHOC₂H₅ H CH₃ m.p. [° C.]: 89-98 5.8 HO 2 (CH₂)₂ CHOC₂H₅ H CH₃ m.p. [° C.]: 150 5.9 HO 0 (CH₂)₂ CHOiPr H CH₃ m.p. [° C.]: 138 5.10 HO 2 (CH₂)₂ CHOiPr H CH₃ m.p. [° C.]: 142 5.11 HO 0 (CH₂)₂ C═NOC₂H₅ H CH₃ m.p. [° C.]: 166 5.12 HO 2 (CH₂)₂ C═NOC₂H₅ H CH₃ m.p. [° C.]: 198 5.13 HO 0 (CH₂)₂ C═NOCH₂CH═CHCl H CH₃ m.p. [° C.]: 163 5.14 HO 2 (CH₂)₂ C═NOCH₂CH═CHCl H CH₃ m.p. [° C.]: 174 5.15 HO 0 (CH₂)₂ C═NOCH₂C₆H₅ H CH₃ m.p. [° C.]: 178 5.16 HO 2 (CH₂)₂ C═NOt-Bu H CH₃ m.p. [° C.]: 217 5.17 H₃CO 0 (CH₂)₂ C(CH₃)₂ H CH₃ m.p. [° C.]: 63-65 5.18 HO 2 (CH₂)₂ CHOCH₃ H Cl m.p. [° C.]: 137-139 5.19 HO 2 (CH₂)₂ C═NOC₂H₅ H Cl m.p. [° C.]: 205 5.20 HO 0 (CH₂) CHOCH₃ H CH₃ ¹H NMR, 300 MHz (d⁶-DMSO): δ [ppm] = 13.0(1H, s), 7.55(1H, d), 7.25 (1H, d), 5.10(1H, s), 3.62(1H, m), 3.42(1H, m), 3.41(3H, s), 2.42(3H, s) 5.21 HO 2 (CH₂) CHOCH₃ H CH₃ ¹H NMR, 300 MHz (d⁶-DMSO): δ [ppm] = 13.5(1H, bs), 8.10(1H, d), 7.60 (1H, d), 5.18(1H, m), 4.07(1H, m), 3.75(1H, m), 3.40(3H, s), 2.70(3H, s) 5.22 HO 2 (CH₂)₂ C═O H Cl ¹H NMR, 300 MHz (d⁶-DMSO): δ [ppm] = 14.2(1H, bs), 8.10(1H, d), 7.98 (1H, d), 4.13(2H, m), 3.30 (2H, m) 5.23 HO 0 (CH₂)₂ C═O H Cl ¹H NMR, 300 MHz (d⁶-DMSO): δ [ppm] = 13.9(1H, bs), 8.10(1H, d), 7.52 (1H, d), 3.41(2H, m), 2.90 (2H, m) 5.24 H₃CO 0 (CH₂)₂ CHOCH₃ H CH₃ ¹H NMR, 400 MHz (CDCl₃): δ [ppm] = 7.46, 7.13, 4.28, 3.87, 3.38, 3.30, 2.90, 2.48, 2.39, 1.91 5.25 H₃CO 0 (CH₂)₂ CHOC₂H₅ H CH₃ m.p. [° C.]: 94-98 5.26 H₃CO 0 (CH₂)₂ CHOipropyl H CH₃ ¹H NMR, 250 MHz (CDCl₃): δ [ppm] = 7.47, 7.17, 4.48, 3.88, 3.79, 3.29, 2.90, 2.48, 2.29, 1.97, 1.21 5.27 HO 1 (CH₂)₂ C═O H CH₃ m.p. [° C.]: 98(decomp.) 5.28 H₃CO 0 CH═CH C═O H CH₃ m.p. [° C.]: 128-130 5.29 HO 0 CH═CH C═O H CH₃ ¹H NMR, 250 MHz (d⁶-DMSO): δ [ppm] = 13.52, 8.48, 8.30, 7.87, 7.03, 2.66 5.30 HO 0 (CH₂)₂ C═NOtbutyl H CH₃ m.p. [° C.]: 217 5.31 HO 2 (CH₂)₂ C═NOC₂H₅ H Cl m.p. [° C.]: 205 5.32 HO 0 (CH₂)₂ C(CH₃)₂ H CH₃ m.p. [° C.]: 212 5.33 HO 0 (CH₂)₂ CH₂ H CH₃ m.p. [° C.]: 155 5.34 HO 0 (CH₂)₂ CH(C₆H₅) H CH₃ m.p. [° C.]: 175 5.35 HO 2 (CH₂)₂ CH₂ H CH₃ m.p. [° C.]: 204 5.36 H₃CO 0 (CH₂)₂ CH(C₆H₅) H CH₃ m.p. [° C.]: 103 5.37 HO 2 (CH₂)₂ CH(C₆H₅) H CH₃ m.p. [° C.]: 145 5.38 HO 0 (CH₂)₂ CHSC₆H₅ H CH₃ m.p. [° C.]: 77 5.39 HO 2 (CH₂)₂ CHSO₂C₆H₅ H CH₃ m.p. [° C.]: 239 5.40 HO 0 (CH₂)₂ C═O Cl Cl ¹H NMR, 250 MHz (CDCl₃): δ [ppm] = 7.69, 3.31, 3.01 5.41 HO 2 (CH₂)₂ C═O Cl Cl ¹H NMR, 250 MHz (d⁶-DMSO): δ [ppm] = 8.04, 4.16, 3.31 5.42 H₃CO 0 (CH₂)₂ CHOH Cl Cl ¹H NMR, 250 MHz (CDCl₃): δ [ppm] = 7.50, 5.20, 4.92, 3.36, 2.89, 2.53, 1.85 5.43 HO 2 (CH₂)₂ CHOH Cl Cl ¹H NMR, 250 MHz (d⁶-DMSO): δ [ppm] = 8.03, 6.96, 5.08, 3.87, 3.62, 2.54, 2.37 5.44 HO 0 (CH₂)₂ CHOH H CH₃ m.p. [° C.]: 209

TABLE 5a Intermediates

No. T n R¹² R¹³ R²¹ R²² Y L M Physical data 5.45 H₃CO 0 CH₃ CH₃ H H C═O H CH₃ ¹H NMR, 270 MHz (CDCl₃): δ [ppm] = 8.02, 7.50, 3.92, 3.09, 2.50, 1.33 5.46 H₃CO 0 H CH₃ H H C═O H CH₃ m.p. [° C.]: 79 5.47 H₃CO 0 CH₃ CH₃ H H CHOCH₃ H CH₃ ¹H NMR, 270 MHz (CDCl₃): δ [ppm] = 7.44, 7.02, 3.89, 3.59, 3.33, 3,28, 2.50, 2.48, 1.21, 0.88 5.48 H₃CO 0 H H CH₃ H C═O H CH₃ m.p. [° C.]: 83 5.49 H₃CO 0 H H CH₃ H CHOCH₃ H CH₃ ¹H NMR, 270 MHz (CDCl₃): δ [ppm] = 7.46, 7.11, 4.31, 3.89, 3.65, 3.37, 2.48, 2.44, 1.64, 1.44 5.50 HO 0 H CH₃ H H CHOCH₃ H CH₃ m.p. [° C.]: 124 5.51 HO 0 CH₃ CH₃ H H CHOCH₃ H CH₃ m.p. [° C.]: 168 5.52 HO 0 H H CH₃ H CHOCH₃ H CH₃ m.p. [° C.]: 145 5.53 HO 2 H CH₃ H H CHOCH₃ H CH₃ m.p. [° C.]: 184 (trans) 5.54 HO 2 CH₃ CH₃ H H CHOCH₃ H CH₃ m.p. [° C.]: 161 5.55 HO 2 H H CH₃ H CHOCH₃ H CH₃ m.p. [° C.]: 182

Preparation of the End Products

1. 1,3-Dimethyl-4-(8-methyl-1,1-dioxothiochroman-4-one-7-carbonyl)-5-hydroxypyrazole

a) 17.4 g (0.0685 mmol) of 8-methyl-1,1-dioxothiochroman-4-one-7-carboxylic acid are dissolved in 170 ml of toluene, the mixture is treated with one drop of dimethylformamide, and 8.96 g (0.0753 mol) of thionyl chloride are added. After the reaction mixture has been refluxed for 4 hours, it is concentrated. The reaction product is directly reacted further.

Yield: 18.6 g (99% of theory) of 8-methyl-1,1-dioxothiochroman-4-one-7-carbonyl chloride

b) 0.82 g (7.3 mmol) of 1,3-dimethylpyrazolone and 0.74 g (7.3 mmnol) of triethylamine are dissolved in 10 ml of acetonitrile. 2.0 g (7.3 mmol) of acid chloride from a), dissolved in 20 ml of acetonitrile, are added dropwise to this mixture. The mixture is stirred for one hour at room temperature. 0.42 g (4.9 mmol) of acetonecyanohydrin and 3.7 g (36.7 mmol) of triethylamine are then added. The mixture is stirred for 6 hours. work-up is carried out by adding 2N hydrochloric acid and extracting the mixture using ethyl acetate. The organic phase is then washed using sodium carbonate solution, the aqueus phase is acidified, and the precipitate which forms is filtered off with suction and dried.

Yield: 0.2 g (8% of theory) of 1,3-dimethyl-4-(8-methyl-1,1-dioxothiochroman-4-one-7-carbonyl)-5-hydroxypyrazole, melting point: 83° C.

2. 7-(1,3-dimethyl-5-hydroxypyrazole-4-carbonyl)-8-methylthiochroman-4-one O-ethyloxime

1 g (3.77 mnmol) of 7-carboxy-8-methylthiochroman-4-one O-ethyloxime are stirred for 2 hours at RT in tert-amyl alcohol together with 0.46 g (4.07 mmol) of 1,3-dimethylpyrazolone and 0.84 g (4.07 mmol) of dicyclohexylcarbodiimide (DCC). 0.78 g (5.66 mmol) of potassium carbonate are subsequently added, and the mixture is heated at 90° C. and stirred for 5 hours at this temperature. It is worked up by stirring the reaction batch into water followed by extraction using ethyl acetate. The organic phase is discarded. The uoaqueus phase is acidified using HCl and the product of interest is extracted using ethyl acetate. The extractant is removed. The product is purified by chromatography.

Yield: 0.35 g (26% of theory) of 7-(1,3-dimethyl-5-hydroxypyrazole-4-carbonyl)-8-methylthio-chroman-4-one O-ethyloxime; ¹H NMR (CDCl₃): δ [ppm]=7.95 (1H, d), 6.99 (1H, d), 4.28 (2H, q), 3.69 (3H, s), 3.10 (2H, m), 2.97 (2H, m), 2.30 (3H, s), 1.75 (3H, s), 1.38 (3H, tr).

3. 7-(1,3-dimethyl-5-hydroxypyrazole-4-carbonyl)-8-methyl-1,1-dioxothiochroman

0.35 g (1 mmol) of 1,3-dimethyl-4-(8-methylthiochroman-4-one-7-carbonyl O-ethyloxime)-5-hydroxypyrazole are introduced into the reaction vessel together with 5 ml of acetic acid and one spatula tip full of sodium tungstate and the mixture is heated at 50° C. 0.24 g (2.1 mmol) of 30% strength hydrogen peroxide solution is then added and the mixture is stirred for 4 hours. Water is then added and the mixture is extracted using ethyl acetate. The organic phase is washed using thiosulfate solution and evaporated on a rotary evaporator.

Yield: 0.35 g (89% of theory) of 7-(1,3 dimethyl-5-hydroxypyrazole-4-carbonyl)-8-methyl-1,1-dioxo-thio-chroman O-ethyloxime)-5-hydroxypyrazole; ¹H NMR (CDCl₃): δ [ppm]=9.90 (1H, bs), 8.12 (1H, d), 7.35 (1H, d), 4.32 (2H, q), 3.65 (3H, s), 3.44 (4H, m), 2.70 (3H, s), 1.73 (3H, s), 1.38 (3H, tr).

TABLE 6 Compounds of the formula

No. R¹⁵ R¹⁶ R¹⁷ n X Y L M M.p. [° C.] 6.1 CH₃ CH₃ H 2 (CH₂)₂ C═O H CH₃ 83 6.2 CH₃ CH₃ H 2 (CH₂)₂ CHOCH₃ H CH₃ 85 6.3 CH₃ CH₃ H 2 (CH₂)₂ CHOC₂H₅ H CH₃ 75 6.4 CH₃ CH₃ H 2 (CH₂)₂ CHOiPr H CH₃ 82 6.5 CH₃ CH₃ H 2 (CH₂)₂ C═NOC₂H₅ H CH₃ 189-191 6.6 C₂H₅ H H 2 (CH₂)₂ C(CH₃)₂ H CH₃ 89-91 6.7 C₂H₅ H H 2 (CH₂)₂ CHOCH₃ H CH₃ 64 6.8 C₂H₅ H H 0 CH═CH C═O H CH₃ 135 6.9 C₂H₅ H H 2 (CH₂)₂ CH₂ H CH₃ 162 6.10 C₂H₅ H H 0 (CH₂)₂ CH(C₆H₅) H CH₃ 132-133 6.11 C₂H₅ H H 2 (CH₂)₂ CH(C₆H₅) H CH₃ 106 6.12 C₂H₅ H H 2 (CH₂)₂ CHNHOC₂H₅ H CH₃ 74 6.13 C₂H₅ H H 2 (CH₂)₂ CHSO₂C₆H₅ H CH₃ 119 6.14 C₂H₅ R SO₂C₃H₇ 2 (CH₂)₂ C(CH₃)₂ H CH₃ 93 6.15 C₂H₅ H SO₂-(p- 2 (CH₂)₂ C(CH₃)₂ H CH₃ 141 (decomp.) CH₃—C₆H₄) 6.16 C₂H₅ H SO₂C₄H₉ 2 (CH₂)₂ C(CH₃)₂ H CH₃ ¹H NMR(250 MHz, CDCl₃, δ in ppm): 7.48, 7.42, 7.37, 4.30, 4.21, 3.80, 3.47, 3.11, 2.86, 2.38, 2.04, 1.47, 1.02, 0.96

TABLE 7

No. R¹⁵ R¹⁶ R¹⁷ n R¹² R¹³ R²¹ R²² Y L M M.p. [° C.] 7.1 C₂H₅ H H 2 H H CH₃ H CHOCH₃ H CH₃ 74-77 7.2 C₂H₅ H H 2 H CH₃ H H CHOCH₃(cis) H CH₃ 72

The compounds I and their agriculturally useful salts—both as isomer mixtures and in the form of the pure isomers—are suitable as herbicides. The herbicidal compositions comprising I effect very good control of vegetation on non-crop areas, especially at high rates of application. In crops such as wheat, rice, maize, soya beans and cotton, they act against broad-leaved weeds and grass weeds without substantially damaging the crop plants. This effect is observed mainly at low rates of application.

Taking into consideration the versatility of the application method, the compounds I or compositions comprising them can also be employed in a further number of crop plants for eliminating undesirable plants. Examples of suitable crops are the following:

Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris spec. altissima, Beta vulagris spec. rapa, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. silvestris, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica), Cucumis sativus, Cynodon dactylon, Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgare, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spec., Manihot esculenta, Medicago sativa, Musa spec., Nicotiana tabacum (N. rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spec., Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Ribes sylestre [sic], Ricinus communis, Saccharum officinarum, Secale cereale, Solanum tuberosum, Sorghum bicolor (s. vulgare), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticum durum, Vicia faba, Vitis vinifera, Zea mays.

Moreover, the compounds I can also be used in crops which have been made tolerant to the action of herbicides by means of breeding, including genetic engineering methods.

The herbicidal compositions or the active ingredients can be applied pre- or post-emergence. If the active ingredients are less well tolerated by certain crop plants, application techniques can be used where the herbicidal compositions are sprayed, with the aid of the spraying apparatus, in such a way that the active ingredients come into as little contact as possible with the leaves of the sensitive crop plants while reaching the leaves of undesirable plants which grow underneath, or the naked soil surface (post-directed, lay-by).

The compounds I or the herbicidal compositions comprising them can be used for example in the form of ready-to-spray aqueous solutions, powders, suspensions, also highly concentrated aqueus oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, materials for spreading or granules by means of spraying, atomizing, dusting, spreading or pouring. The use forms depend on the intended purposes; in any case, they should guarantee the finest possible distribution of the active ingredients according to the invention.

Suitable inert additives are mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, eg. paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, alkylated benzenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, or strongly polar solvents such as N-methylpyrrolidone or water.

Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water. To prepare emulsions, pastes or oil dispersions, the substrates [sic], as such or dissolved in an oil or solvent, can be homogenized in water by means of wetting agent, tackifier, dispersant or emulsifier. However, it is also possible to prepare concentrates composed of active ingredient, wetting agent, tackifier, dispersant or emulsifier and, if desired, solvent or oil, and these concentrates are suitable for dilution with water.

Suitable surfactants (adjuvants) are the alkali metal salts, alkaline earth metal salts and ammonium salts of aromatic sulfonic acids, eg. ligno-, phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl- and alkylarylsulfonates, alkyl sulfates, lauryl ether sulfates and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols, and of fatty alcohol glycol ether, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphthalene, or of the naphthalenesulfonic acids, with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenyl polyglycol ethers, tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene alkyl ethers, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignosulfite waste liquors or methylcellulose.

Powders, materials for spreading and dusts can be prepared by mixing or grinding the active ingredients together with a solid carrier.

Granules, eg. coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers. Solid carriers are mineral earths such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powder or other solid carriers.

The concentrations of the active ingredients I in the ready-to-use preparations can be varied within wide ranges. In general, the formulations comprise from 0.001 to 98% by weight, preferably 0.01 to 95% by weight, of at least one active ingredient. The active ingredients are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum).

The compounds I according to the invention can be formulated for example as follows:

I. 20 parts by weight of the compound No. 6.1 are dissolved in a mixture composed of 80 parts by weight of alkylated benzene, 10 parts by weight of the adduct of 8 to 10 mol of ethylene oxide to 1 mol of oleic acid N-monoethanolamide, 5 parts by weight of calcium dodecylbenzenesulfonate and 5 parts by weight of the adduct of 40 mol of ethylene oxide to 1 mol of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which comprises 0.02% by weight of the active ingredient.

II. 20 parts by weight of the compound No. 6.2 are dissolved in a mixture composed of 40 parts by weight of cyclohexanone, parts by weight of isobutanol, 20 parts by weight of the adduct of 40 mol of isooctylphenol [lacuna] and 10 parts by weight of the adduct of 40 mol of ethylene oxide to 1 mol of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which comprises 0.02% by weight of the active ingredient.

III. 20 parts by weight of the active ingredient No. 6.3 are dissolved in a mixture composed of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction of boiling point 210 to 80° C. [sic] and 10 parts by weight of the adduct of 40 mol of ethylene oxide to 1 mol of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which comprises 0.02% by weight of the active ingredient.

IV. 20 parts by weight of the active ingredient No. 6.4 are mixed thoroughly with 3 parts by weight of sodium diisobutylnaphthalene-a-sulfonate [sic], 17 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 60 parts by weight of pulverulent silica gel and the mixture is ground in a hammer mill. Finely distributing the mixture in 20,000 parts by weight of water gives a spray mixture which comprises 0.1% by weight of the active ingredient.

V. 3 parts by weight of the active ingredient No. 6.5 are mixed with 97 parts by weight of finely divided kaolin. This gives a dust which comprises 3% by weight of the active ingredient.

VI. 20 parts by weight of the active ingredient No. 6.8 are mixed intimately with 2 parts by weight of calcium dodecylbenzenesulfonate, 8 parts by weight of fatty alcohol polyglycol ether, 2 parts by weight of the sodium salt of a phenol/urea/formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil. This give a stable oily dispersion.

VII. 1 part by weight of the active ingredient No. 6.9 is dissolved in a mixture composed of 70 parts by weight of cyclohexanone, 20 parts by weight of ethoxylated isooctylphenol and 10 parts by weight of ethoxylated castor oil. This gives a stable emulsion concentrate.

VIII. 1 part by weight of the active ingredient No. 6.10 is dissolved in a mixture composed of 80 parts by weight of cyclohexanone and 20 parts by weight of Wettol® EM 31 (=non-ionic emulsifier based on ethoxylated castor oil). This gives a stable emulsion concentrate.

To widen the spectrum of action and to achieve synergistic effects, the pyrazol-4-ylbenzene derivatives I may be mixed with a large number of representatives of other groups of herbicidal or growth-regulating active ingredients and then be applied together. Examples of suitable components in the mixtures are 1,2,4-thiadiazoles, 1,3,4-thiadiazoles, amides, aminophosphoric acid and its derivatives, aminotriazoles, anilides, aryloxy/hetaryloxyalkanoic acids and their derivatives, benzoic acid and its derivatives, benzothiadiazinones, 2-(hetaroyl/aroyl)-1,3-cyclohexanedione, heteroaryl aryl ketones, benzylisoxazolidinones, meta-CF₃-phenyl derivatives, carbamates, quinolinecarboxylic acid and its derivatives, chloroacetanilides, cyclohexane-1,3-dione derivatives, diazins, dichloropropionic acid and its derivatives, dihydrobenzofurans, dihydrofuran-3-ones, dinitroanilines, dinitrophenols, diphenyl ethers, dipyridyls, halocarboxylic acids and their derivatives, ureas, 3-phenyluracils, imidazoles, imidazolinones, N-phenyl-3,4,5,6-tetrahydrophthalimides, oxadiazoles, oxiranes, phenols, aryloxy- and hetaryloxyphenoxypropionic esters, phenylacetic acid and its derivatives, 2-phenylpropionic acid and its derivatives, pyrazoles, phenylpyrazoles, pyridazines, pyridinecarboxylic acid and its derivatives, pyrimidyl ethers, sulfonamides, sulfonylureas, triazines, triazinones, triazolinones, triazolecarboxamides and uracils.

It may furthermore be advantageous to apply the compounds I, alone or in combination with other herbicides, also together with further crop protection agents, for example with pesticides or agents for controlling phytopathogenic fungi or bacteria. Also of interest is the miscibility with mineral salt solutions, which are employed for treating nutrient and trace element deficiencies. Non-phytotoxic oil and oil concentrates may also be added.

Depending on the intended aim, the season, the target plants and the growth stage, the application rates are from 0.001 to 3.0, preferably 0.01 to 1.0, kg of active ingredient (a.i.)/ha.

Use Examples

The herbicidal action of the pyrazol-4-yl-benzoyl derivatives of the formula I was demonstrated by greenhouse experiments:

The culture containers used were plastic flowerpots containing loamy sand with approximately 3.0% of humus as the substrate. The seeds of the test plants were sown separately for each species.

For the pre-emergence treatment, the active ingredients which had been suspended or emulsified in water were applied directly after sowing by means of finely distributing nozzles. The containers were irrigated gently to promote germination and growth and subsequently covered with translucent plastic hoods until the plants had rooted. This cover causes uniform germination of the test plants, unless this was adversely affected by the active ingredients.

For the post-emergence treatment, the test plants were first grown to a plant height of 3 to 15 cm, depending on the growth habit, and only then treated with the active ingredients which had been suspended or emulsified in water. To this end, the test plants were either sown directly and grown in the same containers or first grown separately as seedlings and transplanted into the test containers a few days prior to treatment. The rate of application for the post-emergence treatment was 0.5 or 0.25 kg of a.i./ha.

Depending on the species, the plants were kept at from 10 to 25° C. or 20 to 35° C. The test period extended over 2 to 4 weeks. During this time, the plants were tended, and their response to the individual treatments was evaluated.

Evaluation was carried out using a scale from 0 to 100. 100 means no emergence of the plants or complete destruction of at least the aerial parts and 0 means no damage or normal course of growth.

The plants used in the greenhouse experiments were composed of the following species:

Scientific Name Common Name Zea mays Indian corn Chenopodium album lambsquarters (goosefoot) Sinapis alba white mustard Solanum nigrum black nightshade

Scientific Name Common Name Zea mays Indian corn Chenopodium album lambsquarters (goosefoot) Sinapis alba white mustard Solanum nigrum black nightshade 

We claim:
 1. A pyrazol-4-yl-benzoyl compound of the formula I

where the substituents have the following meanings: L, M are hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, it being possible for these groups to be unsubstituted or substituted by one to five halogen atoms or C₁-C₄-alkoxy; halogen, cyano, nitro, a group —(A)_(m)—S(O)_(n)R¹ or a group —(A)_(m)—CO—R²; Y is

or is oxygen or sulfur; X is CR¹²R¹³, CR¹²R¹³—CR²¹R²² or CR¹²═CR¹³; the bond between X and Y can be saturated or unsaturated; A is oxygen or NR¹⁴; m is zero or one; n is two; R¹ is C₁-C₄-alkyl, C₁-C₄-haloalkyl or NR¹⁴; R² is C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy or NR¹⁴; R³ is hydrogen, —NR⁹R⁴; C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₂-C₆-alkenyl, C₂-C₆-haloalkenyl, C₂-C₆-alkynyl; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; unsubstituted or substituted benzyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; unsubstituted or substituted benzyloxy, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; R⁴ is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C═O—NR¹⁴; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; unsubstituted or substituted benzyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; R⁹ is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C═O—NR¹⁴; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; unsubstituted or substituted benzyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; R⁵, R⁶ independently of one another are hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₁-C₄-haloalkyl, C₂-C₆-haloalkenyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; unsubstituted or substituted benzyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; R⁷ is hydrogen, C₁-C₆-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of one to three halogens, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy and nitro; R⁷ and R²¹ or R⁷ and R¹² can form a bond; R⁸ is hydrogen, C₁-C₆-alkyl, C₁-C₄-haloalkyl, unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; unsubstituted or substituted benzyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; R¹⁰, R¹¹ independently of one another are hydrogen, C₁-C₆-alkyl; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of one to three halogens, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy and nitro; R¹⁰ and R¹² or R¹⁰ and R²¹ can form a bond; R¹⁰ and R¹¹ together can form a 1,4-dioxabutane-1,4-diyl, 1,3-dioxabutane-1,4-diyl, 1,5-dioxapentane-1,5-diyl, 1,3-dioxapentane-1,5-diyl or 2,4-dioxapentane-1,5-diyl chain which is substituted by hydrogen or C₁-C₄-alkyl; R¹², R¹³ independently of one another are hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; R¹⁴ is C₁-C₄-alkyl; R²¹ is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; R²² is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; Q is a pyrazole ring, linked in the 4-position, of the formula II

where R¹⁵ is C₁-C₄-alkyl, R¹⁶ is hydrogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl and R¹⁷ is hydrogen, C₁-C₄-alkylsulfonyl, phenylsulfonyl or alkylphenylsulfonyl, or an agriculturally useful salt thereof.
 2. A pyrazol-4-ylbenzoyl compound of the formula Ia

where L is hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, C₁-C₄-haloalkylthio, C₁-C₄-alkylsulfonyl, halogen, nitro or cyano, M is hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, C₁-C₄-haloalkylthio, C₁-C₄-alkylsulfonyl, halogen, nitro or cyano, n is two; X is CR¹²R¹³, CR¹²R¹³—CR²¹R²² or CR¹²═CR¹³; Y is

or is oxygen or sulfur; R³ is hydrogen, —NR⁹R⁴; C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₂-C₆-alkenyl, C₂-C₆-haloalkenyl, C₂-C₆-alkynyl; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; unsubstituted or substituted benzyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; unsubstituted or substituted benzyloxy, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; R⁴ is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C═O—NR¹⁴; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; unsubstituted or substituted benzyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; R⁹ is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C═O—NR¹⁴; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; unsubstituted or substituted benzyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; R⁵, R⁶ independently of one another are hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₁-C₄-haloalkyl, C₂-C₆-haloalkenyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; unsubstituted or substituted benzyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; R⁷ is hydrogen, C₁-C₆-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of one to three halogens, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy and nitro; R⁷ and R²¹ or R⁷ and R¹² can form a bond; R⁸ is hydrogen, C₁-C₆-alkyl, C₁-C₄-haloalkyl, unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; unsubstituted or substituted benzyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; R¹⁰, R¹¹ independently of one another are hydrogen, C₁-C₆-alkyl; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of one to three halogens, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy and nitro; R¹⁰ and R¹² or R¹⁰ and R²¹ can form a bond; R¹⁰ and R¹¹ together can form a 1,4-dioxabutane-1,4-diyl, 1,3-dioxabutane-1,4-diyl, 1,5-dioxapentane-1,5-diyl, 1,3-dioxapentane-1,5-diyl or 2,4-dioxapentane-1,5-diyl chain which is substituted by hydrogen or C₁-C₄-alkyl; R¹², R¹³ independently of one another are hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; R¹⁴ is C₁-C₄-alkyl; R²¹ is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; R²² is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; Q is a pyrazole ring, linked in the 4-position, of the formula II

where R¹⁵ is C₁-C₄-alkyl, R¹⁶ is hydrogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl and R¹⁷ is hydrogen, C₁-C₄-alkylsulfonyl, phenylsulfonyl or alkylphenylsulfonyl, or an agriculturally useful salt thereof.
 3. A pyrazol-4-ylbenzoyl compound of the formula Ib

where L is C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, halogen, nitro or cyano, M is hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, halogen, nitro or cyano, n is two; X is CR¹²R¹³, CR¹²R¹³R²¹R²² or CR¹²═CR¹³; Y is

or is oxygen or sulfur; R³ is hydrogen, —NR⁹R⁴; C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₂-C₆-alkenyl, C₂-C₆-haloalkenyl, C₂-C₆-alkynyl; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; unsubstituted or substituted benzyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; unsubstituted or substituted benzyloxy, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; R⁴ is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C═O—NR¹⁴; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; unsubstituted or substituted benzyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; R⁹ is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C═O—NR¹⁴; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; unsubstituted or substituted benzyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; R⁵, R⁶ independently of one another are hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₁-C₄-haloalkyl, C₂-C₆-haloalkenyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; unsubstituted or substituted benzyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; R⁷ is hydrogen, C₁-C₆-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of one to three halogens, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy and nitro; R⁷ and R²¹ or R⁷ and R¹² can form a bond; R⁸ is hydrogen, C₁-C₆-alkyl, C₁-C₄-haloalkyl, unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; unsubstituted or substituted benzyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; R¹⁰, R¹¹ independently of one another are hydrogen, C₁-C₆-alkyl; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of one to three halogens, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy and nitro; R¹⁰ and R¹² or R¹⁰ and R²¹ can form a bond; R¹⁰ and R¹¹ together can form a 1,4-dioxabutane-1,4-diyl, 1,3-dioxabutane-1,4-diyl, 1,5-dioxapentane-1,5-diyl, 1,3-dioxapentane-1,5-diyl or 2,4-dioxapentane-1,5-diyl chain which is substituted by hydrogen or C₁-C₄-alkyl; R¹², R¹³ independently of one another are hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; R¹⁴ is C₁-C₄-alkyl; R²¹ is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; R²² is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; Q is a pyrazole ring, linked in the 4-position, of the formula II

where R¹⁵ is C₁-C₄-alkyl, R¹⁶ is hydrogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl and R¹⁷ is hydrogen, C₁-C₄-alkylsulfonyl, phenylsulfonyl or alkylphenylsulfonyl, or an agriculturally useful salt thereof.
 4. The pyrazol-4-ylbenzoyl compound of the formula I as defined in claim 1 where the radicals L and M are hydrogen, methyl, methoxy, chlorine, cyano, nitro or trifluoromethyl.
 5. A pyrazol-4-ylbenzoyl compound of the formula Ic

where L is hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, halogen, nitro or cyano, M is hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, halogen, nitro or cyano, n is two; Y is

or is oxygen or sulfur; R³ is hydrogen, —NR⁹R⁴; C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₂-C₆-alkenyl, C₂-C₆-haloalkenyl, C₂-C₆-alkynyl; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; unsubstituted or substituted benzyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; unsubstituted or substituted benzyloxy, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; R⁴ is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₂-C₆-alkenyl, C₂-C₄alkynyl, C═O—NR¹⁴; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; unsubstituted or substituted benzyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; R⁹ is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C═O—NR¹⁴; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; unsubstituted or substituted benzyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; R⁵, R⁶ independently of one another are hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₁-C₄-haloalkyl, C₂-C₆-haloalkenyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; unsubstituted or substituted benzyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; R⁷ is hydrogen, C₁-C₆-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of one to three halogens, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy and nitro; R⁷ and R²¹ or R⁷ and R¹² can form a bond; R⁸ is hydrogen, C₁-C₆-alkyl, C₁-C₄-haloalkyl, unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; unsubstituted or substituted benzyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; R¹⁰, R¹¹ independently of one another are hydrogen, C₁-C₆-alkyl; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of one to three halogens, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy and nitro; R¹⁰ and R¹² or R¹⁰ and R²¹ can form a bond; R¹⁰ and R¹¹ together can form a 1,4-dioxabutane-1,4-diyl, 1,3-dioxabutane-1,4-diyl, 1,5-dioxapentane-1,5-diyl, 1,3-dioxapentane-1,5-diyl or 2,4-dioxapentane-1,5-diyl chain which is substituted by hydrogen or C₁-C₄-alkyl; R¹², R¹³ independently of one another are hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; R¹⁴ is C₁-C₄-alkyl; R²¹ is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; R²² is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; Q is a pyrazole ring, linked in the 4-position, of the formula II

where R¹⁵ is C₁-C₄-alkyl, R¹⁶ is hydrogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl and R¹⁷ is hydrogen, C₁-C₄-alkylsulfonyl, phenylsulfonyl or alkylphenylsulfonyl, or an agriculturally useful salt thereof.
 6. A pyrazol-4-ylbenzoyl compound of the formula Id

where L is hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C4-haloalkoxy, halogen, nitro or cyano, M is hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, halogen, nitro or cyano, n is zero, one or two;

or is oxygen or sulfur; R³ is hydrogen, —NR⁹R⁴; C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₂-C₆-alkenyl, C₁-C₆-haloalkenyl, C₂-C₆-alkynyl; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; unsubstituted or substituted benzyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; unsubstituted or substituted benzyloxy, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; R⁴ is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C═O—NR¹⁴; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; unsubstituted or substituted benzyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; R⁹ is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C═O—NR¹⁴; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; unsubstituted or substituted benzyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; R⁵, R⁶ independently of one another are hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₁-C₄-haloalkyl, C₂-C₆-haloalkenyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; unsubstituted or substituted benzyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; R⁷ is hydrogen, C₁-C₆-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of one to three halogens, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy and nitro; R⁷ and R²¹ or R⁷ and R¹² can form a bond: R⁸ is hydrogen, C₁-C₆-alkyl, C₁-C₄-haloalkyl, unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; unsubstituted or substituted benzyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; R¹⁰, R¹¹ independently of one another are hydrogen, C₁-C₆-alkyl; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of one to three halogens, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy and nitro; R¹⁰ and R¹² or R¹⁰ and R²¹ can form a bond; R¹⁰ and R¹¹ together can form a 1,4-dioxabutane-1,4-diyl, 1,3-dioxabutane-1,4-diyl, 1,5-dioxapentane-1,5-diyl, 1,3-dioxapentane-1,5-diyl or 2,4-dioxapentane-1,5-diyl chain which is substituted by Hydrogen or C₁-C₄-alkyl; R¹², R¹³ independently of one another are hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; R¹⁴ is C₁-C₄-alkyl; O is a pyrazole ring, linked in the 4-position, of the formula II

where R¹⁵ is C₁-C₄-alkyl, R¹⁶ is hydrogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl and R¹⁷ is hydrogen, C₁-C₄-alkylsulfonyl, phenylsulfonyl or alkylphenylsulfonyl, or an agriculturally useful salt thereof.
 7. A pyrazol-4-ylbenzoyl compound of the formula Ie

where L is hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, halogen, nitro or cyano, M is hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, halogen, nitro or cyano, n is two; Y is

or is oxygen or sulfur; R³ is hydrogen, —NR⁹R⁴; C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₂-C₆-alkenyl, C₂-C₆-haloalkenyl, C₂-C₆-alkynyl; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; unsubstituted or substituted benzyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; unsubstituted or substituted benzyloxy, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; R⁴ is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₂-C₈-alkenyl, C₂-C₆-alkynyl, C═O—NR¹⁴; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; unsubstituted or substituted benzyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; R⁹ is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C═O—NR¹⁴; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; unsubstituted or substituted benzyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; R⁵, R⁶ independently of one another are hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₁-C₄-haloalkyl, C₂-C₆-haloalkenyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; unsubstituted or substituted benzyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; R⁷ is hydrogen, C₁-C₆-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of one to three halogens, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy and nitro; R⁷ and R²¹ or R⁷ and R¹² can form a bond; R⁸ is hydrogen, C₁-C₆-alkyl, C₁-C₄-haloalkyl, unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; unsubstituted or substituted benzyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; R¹⁰, R¹¹ independently of one another are hydrogen, C₁-C₆-alkyl; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of one to three halogens, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy and nitro; R¹⁰ and R¹² or R¹⁰ and R²¹ can form a bond; R¹⁰ and R¹¹ together can form a 1,4-dioxabutane-1,4-diyl, 1,3-dioxabutane-1,4-diyl, 1,5-dioxapentane-1,5-diyl, 1,3-dioxapentane-1,5-diyl or 2,4-dioxapentane-1,5-diyl chain which is substituted by hydrogen or C₁-C₄-alkyl; R¹², R¹³ independently of one another are hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy; unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; R¹⁴ is C₁-C₄-alkyl; Q is a pyrazole ring, linked in the 4-position, of the formula II

where R¹⁵ is C₁-C₄-alkyl, R¹⁶ is hydrogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl and R¹⁷ is hydrogen, C₁-C₄-alkylsulfonyl, phenylsulfonyl or alkylphenylsulfonyl, or an agriculturally useful salt thereof.
 8. The pyrazol-4-ylbenzoyl compound of the formula I as defined in claim 1 where n is two and Y is


9. A process for the preparation of a compound of the formula I as defined in claim 1, which comprises acylating a pyrazole of the formula IIa

with an acid chloride of the formula IIIa or an acid IIIb

and subjecting the acylation product to a rearrangement reaction in the presence of a catalyst to give the compound I.
 10. A herbicidal composition comprising at least one pyrazol-4-ylbenzoyl compound of the formula I as defined in claim 1 and customary inert additives.
 11. A method of controlling undesirable vegetation, which comprises treating the plants or their environment with a herbicidally active amount of a pyrazol-4-ylbenzoyl compound of the formula I as defined in claim
 1. 12. The pyrazol-4-ylbenzoyl compound of the formula I as defined in claim 1 where X is CR¹²R¹³ or CR¹²═CR¹³.
 13. The pyrazol-4-ylbenzoyl compound of the formula I as defined in claim 1 wherein Y is

or is oxygen or sulfur.
 14. The pyrazol-4-ylbenzoyl compound of the formula I as defined in claim 1 wherein Y is

and R⁸ is C₁-C₄-haloalkyl, unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; unsubstituted or substituted benzyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro.
 15. The pyrazol-4-ylbenzoyl compound of the formula Ia as defined in claim 2 where X is CR¹²R¹³ or CR¹²═CR¹³.
 16. The pyrazol-4-ylbenzoyl compound of the formula Ib as defined in claim 3 where X is CR¹²R¹³ or CR¹²═CR¹³.
 17. The pyrazol-4-ylbenzoyl compound of the formula Ic as defined in claim 5 wherein Y is

or is oxygen or sulfur.
 18. The pyrazol-4-ylbenzoyl compound of the formula Ic as defined in claim 5 wherein Y is

and R⁸ is C₁-C₄-haloalkyl, unsubstituted or substituted phenyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro; unsubstituted or substituted benzyl, wherein the substituents are selected from the group consisting of C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl, halogen, cyano and nitro. 62 